Carbon Dioxide Scrubbing Using Ionic Materials

ABSTRACT

One aspect of the present invention relates to amine-functionalized task-specific ionic liquids (TSILs). In certain embodiments, the ionic liquids of the invention comprise beta-hydroxy amines, aryl amines or tertiary amines. The TSILs may be used for gas capture, capitalizing on their non-volatile nature. In certain embodiments, the captured gas is selected from the group consisting of CO 2 , SO 2 , CS 2 , and NO 2 . Another aspect of the present invention relates to a library of CO2-philic salts, which library facilitates reactive gas separation. In certain embodiments, the CO 2 -philic salts are CO 2 -reactive TSILs. In certain embodiments, the CO 2 -philic salts are resinous or plastic in nature.

RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional PatentApplication Ser. No. 60/909,538, filed Apr. 2, 2007; and U.S.Provisional Patent Application Ser. No. 60/990,128, filed Nov. 26, 2007;both of which are hereby incorporated by reference in their entirety.

BACKGROUND OF THE INVENTION

Carbon dioxide is a chemical chimera. Essential to life by virtue of itsrole as the carbon supplier in photosynthesis, it has also come to beregarded as an environmental threat due to its contributions to globalwarming. Likewise, while certain recent work has constructivelyharnessed CO₂ to form novel soft materials, other current researchfocuses on the synthesis of new materials explicitly for achieving CO₂removal when its presence constitutes a nuisance.

The reversible capture of CO₂ is a process of importance in applicationsranging from respiration devices to natural gas sweetening (Stewart, C.;Hessami, M.-A. Energy Conv. Mgmt., 2005, 46, 403; Harrison, D. P.;Silaban, A. Chem. Eng. Comm. 1995, 137, 177). For example, thereversible capture of CO₂ is a prominent feature of schemes for themitigation of causative agents in global warming. Already important inthe purification of natural gas and in breathing-air recirculationsystems, CO₂ capture is achieved on large scales by passing acontaminated gas through an aqueous amine solution, with which theentrained CO₂ reacts (Kohl, A.; Nielsen, R. Gas Purification, 5th ed.,Gulf: Houston, 1997; Chapters 1, 2. and 14). Unfortunately, the processis frustrated by the volatility of the dissolved amines, which aregradually lost into the gas stream. Accordingly, if reactive capture isto be an element of future CO₂ management technologies, there is apressing need to develop systems in which the scavenger is bothaffordable and non-volatile.

One of the most promising new categories of materials for use in CO₂removal is ionic liquids (ILs). At higher pressures, CO₂ has a greaterinnate solubility in many classical ILs than do other gases, makingphysical solvation a potential method of removal. At lower pressures,reactive gas capture by amine-functionalized task-specific ionic liquids(TSILs) is promising. Using these functional salts, it is possible tocapture CO₂ in a fashion akin to commercial scrubbing amines whileavoiding backpressure from the amine and the slow loss of the amine intothe treated gas stream (Bates, E. D. et al. J. Am. Chem. Soc. 2002, 124,4194). Since ionic liquids (ILs) typically lack a detectable vaporpressure, they are conceptually ideal materials for CO₂ capturetechnology (Bates, E. D. et al. J. Am. Chem. Soc. 2002, 124, 4194;Zhang, J. et al. Chem. Eur. J. 2006, 12, 4021; Huang, J. et al. Chem.Comm. 2006, 4027; Anthony, J. L. et al. Int. J. Envir. Tech. Mgmt. 2004,4, 105). However, the scales involved in industrial capture applicationsrequire large amounts of the reactive agents. Moreover, someamine-functionalized TSILs are relatively costly and/or tedious toprepare and purify. Further, these TSILs have or potentially haveproblems with long-term stability.

Accordingly, it is important to find new CO₂-reactive TSILs and relatedsoft ionic materials, especially by co-opting commercially availablecommodity chemicals as starting materials, and assembling them in quick,high-yielding and atom-efficient reactions. Furthermore, since theultimate goal is the development of property-tunable ionic materials forlarge-scale CO₂ scavenging, it is vital to identify alternatives whichcan be made using a procedure that is uncomplicated, economicallyattractive, and capable of quickly producing a large number of materialsfor screening purposes. Specifically, an approach which embodiesattributes of the Kolb, Finn and Sharpless “click” concept (rapid,modular, employing commodity chemicals, highly atom efficient, usingminimal and/or relatively benign solvents, and giving high yields ofproducts useable with little or no purification) is desired (Kolb, H.C.; Finn, M. G.; Sharpless, K. B. Angew. Chem. Int. Ed. 2001, 40, 2004).

SUMMARY OF THE INVENTION

One aspect of the present invention relates to amine-functionalizedtask-specific ionic liquids (TSILs). In certain embodiments, the ionicliquids of the invention comprise 1,3-diamines, beta-hydroxy amines,aryl amines or tertiary amines. The TSILs may be used for gas capture,capitalizing on their non-volatile nature. In certain embodiments, thecaptured gas is selected from the group consisting of CO₂, SO₂, CS₂, andNO₂. In certain embodiments, the captured gas is CO₂.

Another aspect of the present invention relates to a library ofCO₂-philic salts, which library facilitates reactive gas separation. Incertain embodiments, the CO₂-philic salts are CO₂-reactive TSILs.Remarkably, in certain embodiments, the CO₂-philic salts are resinous orplastic in nature.

In certain embodiments, the compounds of the present invention areprepared from commodity chemicals, including but not limited to primaryamines, secondary amines, diamines, sultones, epoxides, aryl amines andquaternary ammonium hydroxides.

In certain embodiments, preparing a compound of the invention comprisesone or more high-yielding, atom-efficient “click” reactions that producewater as the sole byproduct (Kolb, H. C.; Finn, M. G.; Sharpless, K. B.Angew. Chem. Int. Ed. 2001, 40, 2004). In certain embodiments, thenucleophile of this reaction consists of an uncharged Lewis base; i.e.,a compound that contains a lone pair of electrons but has no net charge.In certain embodiments, the nucleophile is a primary, secondary,tertiary amine, or diamine. In certain embodiments, one synthetic stepinvolves the reaction between an amine and a sultone. In certainembodiments, one synthetic step involves the reaction between an amine,or a zwitterion, and an epoxide. In certain embodiments, in onesynthetic step a zwitterion intermediate undergoes simultaneousdeprotonation and ion exchange by reaction of the intermediate with anammonium hydroxide salt or other hydroxide base.

In certain embodiments, a salt of the present invention is hydrophilic.In certain embodiments, a salt of the present invention is an ionicliquid. In certain embodiments, a salt of the present invention is aplastic or resin. In certain embodiments, a salt of the presentinvention is a solid.

Another aspect of this invention is a method for the reversible uptakeof a gas by a salt of the present invention. In certain embodiments, thegas is CO₂. The uptake of CO₂ by any of the salts of the presentinvention, which occurs even when the salts are exposed to air, has beendemonstrated in a variety of fashions. In certain embodiments, after CO₂exposure, qualitative evidence of CO₂ uptake is manifest by an increasein viscosity, solidification, or the development of a frosted appearanceby a resinous or plastic salt of the present invention.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 depicts a generic synthetic scheme for the production of certaincationic and anionic CO₂-philic materials from a zwitterionicintermediate.

FIG. 2 depicts [A] a synthetic scheme for selected CO₂-philic materials;and [B] images showing [1B2A3A] “sliced” and removed in strips from thereaction vessel in which it was prepared as a transparent, somewhattacky, moldable film (using a solvent evaporation approach it can beapplied to the coils of a condenser which is then fitted with gasadapters at each end to create a simple, recyclable, pass-through CO₂absorber).

FIG. 3 depicts the carbonyl region of FTIR spectra of [1B2A3C] before(upper) and after (lower) CO₂ exposure.

FIGS. 4-6 tabulate CO₂ capture data based upon comparative IR spectrabefore and after exposure (the appearance of a peak between 1619-1654cm⁻¹ is diagnostic for the sequestration of CO₂ as carbamate). Theobservance of small peaks (IR) for carbamate even before deliberateexposure to a CO₂ stream apparently results from CO₂ absorption from theair. All compounds were azeotropically dried with benzene and held undervacuum for at least 12 hours. The compounds that are resinous or plasticin nature (indicated in bold print) were also examined for CO₂ captureafter being allowed to saturate with water vapor in a sealed container.

FIGS. 7-8 tabulate the mass changes (at intervals of 1, 4, 7 and 14days) of samples of various salts of the invention stored in a sealedcontainer above a water reservoir.

FIGS. 9-10 depict generic synthetic schemes for certain CO₂-philicmaterials of the present invention which are prepared via a zwitterionicintermediate.

FIGS. 11-20 depict experimental data for the syntheses of variouszwitterions and the syntheses of various TSILs derived from suchzwitterions.

DETAILED DESCRIPTION OF THE INVENTION

One aspect of the present invention relates to amine-functionalizedtask-specific ionic liquids (TSILs) for gas capture, which capitalize onthe non-volatile nature of these salts (see Lee, S.-G. Chem. Commun.2006, 1049; Davis, J. H., Jr. Chemistry Letters 2004, 33, 1072). Incertain embodiments, the amine-functionalized task-specific ionicliquids comprise diamines, beta-hydroxy amines, aryl amines and/ortertiary amines. Zhang has shown that amine-functionalized TSILs neednot be in a bulk liquid form to capture CO₂, but could also do so whensupported on a solid (Zhang, J. et al. Chem. Eur. J. 2006, 12, 4021).Together, these findings support the proposition thatamine-functionalized salts in various forms are promising gas-scavengingmaterials. In certain embodiments, the gas is selected from the groupconsisting of CO₂, SO₂, CS₂, and NO₂. In certain embodiments, the gas isCO₂.

Another aspect of the present invention relates to CO₂-philic salts or alibrary of them, which library is the first created to facilitate areactive gas separation. In certain embodiments, the CO₂-philic saltsare CO₂-reactive TSILs.

Remarkably, in certain embodiments, the CO₂-philic salts are resinous orplastic in nature. Although the low molecular mass organogelation (LMOG)or water-induced formation of IL gels is known (Henderson, D., Holovko,M.; Trokhymchuk, A., Eds. Ionic Soft Matter: Modern Trends in Theory andApplications; NATO Science Series II, 206; Springer: Dordrecht, 2005),the reactions of CO₂ with amine-modified polymers (Henderson, D.,Holovko, M.; Trokhymchuk, A., Eds. Ionic Soft Matter: Modern Trends inTheory and Applications; NATO Science Series II, 206; Springer:Dordrecht, 2005), and the CO₂-induced formation of soft matter (Ohno,H., Ed. Electrochemical Aspects of Ionic Liquids; Wiley: Hoboken, 2005,323-336; Liu, Y. et al. Science, 2006, 313, 958; Rudkevich, D. M.; Xu,H. Chem. Commun. 2005, 2651; George, M.; Weiss, R. G. J. Am. Chem. Soc.2001, 123, 10393), the soft ionic phases of the present invention areremarkable materials for CO₂ capture. The physical states of these softionic phases render them easy to apply to almost any solid surface onwhich they form durable deposits, which surfaces include glass,plastics, textiles and metals.

In certain embodiments, the compounds of the present invention are madefrom commodity chemicals. In certain embodiments, these chemicalsinclude primary amines, secondary amines, diamines, sultones, epoxides,and quaternary ammonium hydroxides. In certain embodiments, theirmodular nature lends them to combinatorial assembly via an inexpensiveprocess.

In certain embodiments, the process comprises one or more high-yielding,atom-efficient “click” reactions that produce water as the solebyproduct (Kolb, H. C.; Finn, M. G.; Sharpless, K. B. Angew. Chem. Int.Ed. 2001, 40, 2004). Remarkably, these reactions require minimal amountsof inexpensive and benign solvents, are frequently rapid, and usuallyrequire no heating or cooling.

In certain embodiments, the materials produced in the present inventionare serviceable for CO₂ capture without purification, which is anenormous advantage for any material being developed for large-scale use.

In certain embodiments, in the context of their function as TSILcomponents, the products of the ring opening have two key features. Akey feature is the creation of a permanent anionic charge in the form ofan alkane sulfonate group. This anion type is charge-diffuse andconsequently poorly basic and poorly nucleophilic, both desirableattributes. Another key feature is the covalent tether between the anionand the amine group that is formed in the reaction.

In certain embodiments, the salts of the present invention arehydrophilic.

In certain embodiments, the salts are ionic liquids.

In certain embodiments, the salts are plastic or resin.

In certain embodiments, the salts are solid.

In certain embodiments, water is removed from the salts by azeotropicdrying and storage under vacuum over solid P₂O₅.

In certain embodiments, water levels as low as about 10%. In certainembodiments, water levels as low as about 4%. In certain embodiments,water levels as low as about 3%. In certain embodiments, water levels aslow as about 2%.

In certain embodiments, the materials that are plastics and resins havevarying capacities to absorb water while retaining their structuralintegrity.

In certain embodiments, these materials resist deliquescence for dayswhen sealed in an atmosphere of water-saturated air.

Another aspect of this invention is the reversible uptake of a gas by amaterial of the present invention.

In certain embodiments, the gas is CO₂. The uptake of CO₂ by any of thesalts of the present invention, which occurs even when the salts areleft open to air, can be demonstrated in a variety of fashions.

In certain embodiments, after CO₂ exposure, qualitative evidence of CO₂uptake may be manifest in a visible increase in the viscosities oroccasional solidification of those that are liquids; and the frostedappearance of those that are resins.

In certain embodiments, TSIL samples charged with indicator dye changefrom sapphire to bright green on exposure to the gas (see MacFarlane, D.R. et al. Chem. Commun. 2006, 1905). In certain embodiments, thedye-charged resins also respond in this fashion, suggesting a potentialfor their development as apply-anywhere colorimetric CO₂ sensors.

Unambiguous evidence of CO₂ binding is provided by FTIR, ¹³C-NMR, andESI-MS. For example, in certain embodiments marked changes in the ¹³Cspectrum of compounds of the invention when treated with a stream of CO₂may be observed; including the appearance of a strong new signal atabout 160 ppm. This new signal is consistent with the CO₂-suppliedcarbon atom of a newly formed carbamate (or, possibly, carbamic acid)group within the anion. In addition, the appearance of a peak between1619-1654 cm⁻¹ in the FTIR is diagnostic for the sequestration of CO₂ ascarbamate (see Pretsch et al. Tables of Spectral Data for StructuralDetermination of Organic Compounds, 2d ed.; Springer: Berlin, 1989;Silverstein et al. Spectrometric Identification of Organic Compounds,5th ed.; Wiley: New York, 1991; Bates, E. D. et al. J. Am. Chem. Soc.2002, 124, 4194; Zhang, J. et al. Chem. Eur. J. 2006, 12, 4021; Liu, Y.et al. Science, 2006, 313, 958; Rudkevich, D. M.; Xu, H. Chem. Commun.2005, 2651; George, M.; Weiss, R. G. J. Am. Chem. Soc. 2001, 123,10393). Further, negative-mode ESI-MS may provide additional evidencefor the covalent incorporation of CO₂ into the anion structure. Further,if the intensity of peaks from the CO₂-containing ions diminishes withresidence time in the mass spectrometer, this would provide furtherverification of the reversibility of the binding.

In certain embodiments, one synthetic step involves the reaction betweenan amine or a phosphine and a sultone. In certain embodiments, thesultone is 1,3-propanesultone. In certain embodiments, the sultone is1,4-butane sultone. In certain embodiments, the sultone is representedby:

In certain embodiments, the sultone and amine or phosphine are combinedto produce a zwitterion intermediate.

In certain embodiments, in one synthetic step the zwitterionintermediate undergoes simultaneous deprotonation and ion exchange byreaction of the intermediate with an ammonium hydroxide or other base.In other embodiments, the zwitterion intermediate undergoes protonationby an acid. See FIG. 1.

In certain embodiments, one synthetic step involves the reaction betweenan amine and a sultone. In certain embodiments, the amine is a primary,secondary, or tertiary amine. In certain embodiments, the reactionbetween the amine and sultone produces a zwitterion represented by:

In certain embodiments, one synthetic step involves the reaction betweena phosphine and a sultone. In certain embodiments, the phosphine has theformula RPH₂ or R₂PH. In certain embodiments, the reaction between thephosphine and sultone produces a zwitterion represented by:

In certain embodiments, the anion in the compounds of the presentinvention has an impact on the properties of the final products. Incertain embodiments, the cation in the compounds of the presentinvention has an impact on the properties of the final products.

In certain embodiments, the resulting intermediates and/or products aredried under vacuum.

In certain embodiments, selected synthetic steps are represented by thefollowing schemes (reactions with primary amines, secondary amines ordiamines):

In certain embodiments, the zwiterionic intermediate can be reacted withan epoxide, as shown the schemes below. In certain embodiments, selectedsynthetic steps are represented by the following scheme:

A variety of zwitterionic intermediates can be used; for example,selected synthetic steps are represented by the following scheme:

While many of the above examples have shown ammonium hydroxide salts, asthe base, reacting with the zwiterionic intermediates, one may also usea phosphonium cation, a heterocyclic (e.g., imidazolium or pyridinium)cation, or in certain circumstances an alkali metal cation or analkaline earth metal cation as the counterion. In certain embodiments,the cations can be metal cations, such as Na, K, Ca, Ba, etc.

While the selected synthentic routes described above have all suggestedreacting hydroxide salts of various cations with the zwitterions, othersynthetic approaches can be envisioned as well, such as zwitteriondeprotonation with strong bases like NaH or BuLi, followed by an ionmetathesis step to exchange the Na or Li for a different cation.

In certain embodiments, the anion in the compounds of the presentinvention is a homotaurine derivatives related to Zwittergent®-typedetergents. Aqueous solutions of taurine/homotaurine capture CO₂ (seeWolfram, A. et al., DE 1071674). However, where the latter incorporatequaternary nitrogen centers arising from tertiary amine induced sultonering-opening, the use of primary amines in certain embodiments of thepresent invention gives rise instead to secondary amine substituents.Interestingly, the presence of both a lone pair and a hydrogen atom onthe nitrogen of the final anion are sometimes features for the captureof CO₂ as a carbamate; accepted as a key mechanism by which scrubbingamines function (Kohl, A.; Nielsen, R. Gas Purification, 5th ed.; Gulf:Houston, 1997; Chapters 1, 2. and 14).

Remarkably, in certain embodiments, the amine-provided alkyl group has anotable impact on the properties of the final products.

In certain embodiments, anions derived from [1A], [1B], [1C], and [1D]are more apt to form the resinous or plastic materials (see FIG. 2A).

DEFINITIONS

For convenience, certain terms employed in the specification, examples,and appended claims are collected here.

The articles “a” and “an” are used herein to refer to one or to morethan one (i.e., to at least one) of the grammatical object of thearticle. By way of example, “an element” means one element or more thanone element.

The term “ionic liquid” or “IL” as used herein means an organic salt orhydrate thereof with a melting point less than about 150° C. In apreferred embodiment, the ionic liquid has a melting point of less thanabout 100° C. In a preferred embodiment, the ionic liquid has a meltingpoint of less than about 50° C. In a preferred embodiment, the ionicliquid has a melting point of less than about room temperature. Theionic liquids of the present invention may comprise one or morecompounds. Thus, the ionic liquid may be a pure compound or may be amixture of compounds. Each compound comprises an anion or a mixture ofanions; and a cation or a mixture of cations.

The term “Lewis base” as used herein is a substance which acts as anelectron pair donor.

The term “electron-withdrawing group” is recognized in the art, anddenotes the tendency of a substituent to attract valence electrons fromneighboring atoms, i.e., the substituent is electronegative with respectto neighboring atoms. A quantification of the level ofelectron-withdrawing capability is given by the Hammett sigma (σ)constant. This well known constant is described in many references, forinstance, J. March, Advanced Organic Chemistry, McGraw Hill BookCompany, New York, (1977 edition) pp. 251-259. The Hammett constantvalues are generally negative for electron donating groups (σ [P]=−0.66for NH₂) and positive for electron withdrawing groups (σ [P]=0.78 for anitro group), σ [P] indicating para substitution. Exemplaryelectron-withdrawing groups include nitro, acyl, formyl, sulfonyl,trifluoromethyl, cyano, chloride, and the like. Exemplaryelectron-donating groups include amino, methoxy, and the like.

The term “charge-diffuse anion” as used herein is a non-Lewis acidcontaining polyatomic anion having a van der Waals volume exceeding 100Å³. Charge-diffuse anions include, for example, boron tetrafluoride,boron tetraphenyl, phosphorus hexafluoride, methanesulfonate,trifluoromethanesulfonate, benzenesulfonate, p-toluenesulfonate,bis(methanesulfonyl)amide, bis(trifluoromethanesulfonyl)amide,bis(benzenesulfonyl)amide or bis(p-toluenesulfonyl)amide.

The term “aliphatic” is an art-recognized term and includes linear,branched, and cyclic alkanes, alkenes, or alkynes. In certainembodiments, aliphatic groups in the present invention are linear orbranched and have from 1 to about 20 carbon atoms.

The term “alkyl” is art-recognized, and includes saturated aliphaticgroups, including straight-chain alkyl groups, branched-chain alkylgroups, cycloalkyl (alicyclic) groups, alkyl substituted cycloalkylgroups, and cycloalkyl substituted alkyl groups. In certain embodiments,a straight chain or branched chain alkyl has about 30 or fewer carbonatoms in its backbone (e.g., C₁-C₃₀ for straight chain, C₃-C₃₀ forbranched chain), and alternatively, about 20 or fewer. Likewise,cycloalkyls have from about 3 to about 10 carbon atoms in their ringstructure, and alternatively about 5, 6 or 7 carbons in the ringstructure.

Unless the number of carbons is otherwise specified, “lower alkyl”refers to an alkyl group, as defined above, but having from one to tencarbons, alternatively from one to about six carbon atoms in itsbackbone structure. Likewise, “lower alkenyl” and “lower alkynyl” havesimilar chain lengths.

The term “bicyclo-ring” as used herein refers to a bridged ring systemsuch as a quinuclidine (shown below).

The term “aralkyl” is art-recognized, and includes alkyl groupssubstituted with an aryl group (e.g., an aromatic or heteroaromaticgroup).

The terms “alkenyl” and “alkynyl” are art-recognized, and includeunsaturated aliphatic groups analogous in length and possiblesubstitution to the alkyls described above, but that contain at leastone double or triple bond respectively.

The term “heteroatom” is art-recognized, and includes an atom of anyelement other than carbon or hydrogen. Illustrative heteroatoms includeboron, nitrogen, oxygen, phosphorus, sulfur and selenium, andalternatively oxygen, nitrogen or sulfur.

The term “aryl” is art-recognized, and includes 5-, 6- and 7-memberedsingle-ring aromatic groups that may include from zero to fourheteroatoms, for example, benzene, naphthalene, anthracene, pyrene,pyrrole, furan, thiophene, imidazole, oxazole, thiazole, triazole,pyrazole, pyridine, pyrazine, pyridazine and pyrimidine, and the like.Those aryl groups having heteroatoms in the ring structure may also bereferred to as “heteroaryl” or “heteroaromatics.” The aromatic ring maybe substituted at one or more ring positions with such substituents asdescribed herein, for example, halogen, azide, alkyl, aralkyl, alkenyl,alkynyl, cycloalkyl, hydroxyl, alkoxyl, amino, nitro, sulfhydryl, imino,amido, phosphonate, phosphinate, carbonyl, carboxyl, silyl, ether,alkylthio, sulfonyl, sulfonamido, ketone, aldehyde, ester, heterocyclyl,aromatic or heteroaromatic moieties, fluoroalkyl (such astrifluoromethyl), cyano, or the like. The term “aryl” also includespolycyclic ring systems having two or more cyclic rings in which two ormore carbons are common to two adjoining rings (the rings are “fusedrings”) wherein at least one of the rings is aromatic, e.g., the othercyclic rings may be cycloalkyls, cycloalkenyls, cycloalkynyls, arylsand/or heterocyclyls.

The terms ortho (o-), meta (m-) and para (p-) are art-recognized andapply to 1,2-, 1,3- and 1,4-disubstituted benzenes, respectively. Forexample, the names 1,2-dimethylbenzene, ortho-dimethylbenzene ando-dimethylbenzene are synonymous.

The terms “heterocyclyl” and “heterocyclic group” are art-recognized,and include 3- to about 10-membered ring structures, such as 3- to about7-membered rings, whose ring structures include one to four heteroatoms.Heterocycles may also be polycycles. Heterocyclyl groups include, forexample, thiophene, thianthrene, furan, pyran, isobenzofuran, chromene,xanthene, phenoxathiin, pyrrole, imidazole, pyrazole, isothiazole,isoxazole, pyridine, pyrazine, pyrimidine, pyridazine, indolizine,isoindole, indole, indazole, purine, quinolizine, isoquinoline,quinoline, phthalazine, naphthyridine, quinoxaline, quinazoline,cinnoline, pteridine, carbazole, carboline, phenanthridine, acridine,pyrimidine, phenanthroline, phenazine, phenarsazine, phenothiazine,furazan, phenoxazine, pyrrolidine, oxolane, thiolane, oxazole,piperidine, piperazine, morpholine, lactones, lactams, such asazetidinones and pyrrolidinones, sultams, sultones, and the like. Theheterocyclic ring may be substituted at one or more positions with suchsubstituents as described above, as for example, halogen, alkyl,aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, amino, nitro,sulfhydryl, imino, amido, phosphonate, phosphinate, carbonyl, carboxyl,silyl, ether, alkylthio, sulfonyl, ketone, aldehyde, ester, aheterocyclyl, an aromatic or heteroaromatic moiety, fluoroalkyl (such astrifluoromethyl), cyano, or the like.

The terms “polycyclyl” and “polycyclic group” are art-recognized, andinclude structures with two or more rings (e.g., cycloalkyls,cycloalkenyls, cycloalkynyls, aryls and/or heterocyclyls) in which twoor more carbons are common to two adjoining rings, e.g., the rings are“fused rings”. Rings that are joined through non-adjacent atoms, e.g.,three or more atoms are common to both rings, are termed “bridged”rings. Each of the rings of the polycycle may be substituted with suchsubstituents as described above, as for example, halogen, alkyl,aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, amino, nitro,sulfhydryl, imino, amido, phosphonate, phosphinate, carbonyl, carboxyl,silyl, ether, alkylthio, sulfonyl, ketone, aldehyde, ester, aheterocyclyl, an aromatic or heteroaromatic moiety, fluoroalkyl (such astrifluoromethyl), cyano, or the like.

The term “carbocycle” is art recognized and includes an aromatic ornon-aromatic ring in which each atom of the ring is carbon. The flowingart-recognized terms have the following meanings “nitro” means —NO₂; theterm “halogen” designates —F, —Cl, —Br or —I; the term “sulfhydryl”means —SH; the term “hydroxyl” means —OH; and the term “sulfonyl” means—SO₂.

The terms “amine” and “amino” are art-recognized and include bothunsubstituted and substituted amines, e.g., a moiety that may berepresented by the general formulas:

wherein R50, R51 and R52 each independently represent a hydrogen, analkyl, an alkenyl, —(CH₂)_(m)—R61, or R50 and R51, taken together withthe N atom to which they are attached complete a heterocycle having from4 to 8 atoms in the ring structure; R61 represents an aryl, acycloalkyl, a cycloalkenyl, a heterocycle or a polycycle; and m is zeroor an integer in the range of 1 to 8. In certain embodiments, only oneof R50 or R51 may be a carbonyl, e.g., R50, R51 and the nitrogentogether do not form an imide. In other embodiments, R50 and R51 (andoptionally R52) each independently represent a hydrogen, an alkyl, analkenyl, or —(CH₂)_(m)—R61. Thus, the term “alkylamine” includes anamine group, as defined above, having a substituted or unsubstitutedalkyl attached thereto, i.e., at least one of R50 and R51 is an alkylgroup.

The term “acylamino” is art-recognized and includes a moiety that may berepresented by the general formula:

wherein R50 is as defined above, and R54 represents a hydrogen, analkyl, an alkenyl or —(CH₂)_(m)—R61, where m and R61 are as definedabove.

The term “amido” is art recognized as an amino-substituted carbonyl andincludes a moiety that may be represented by the general formula:

wherein R50 and R51 are as defined above. Certain embodiments of theamide in the present invention will not include amides which may beunstable.

The term “alkylthio” is art recognized and includes an alkyl group, asdefined above, having a sulfur radical attached thereto. In certainembodiments, the “alkylthio” moiety is represented by one of —S-alkyl,—S-alkenyl, —S-alkynyl, and —S—(CH₂)_(m)—R61, wherein m and R61 aredefined above. Representative alkylthio groups include methylthio,ethylthio, and the like.

The term “carbonyl” is art recognized and includes such moieties as maybe represented by the general formulas:

wherein X50 is a bond or represents an oxygen or a sulfur, and R55represents a hydrogen, an alkyl, an alkenyl, —(CH₂)_(m)—R61 or apharmaceutically acceptable salt, R56 represents a hydrogen, an alkyl,an alkenyl or —(CH₂)_(m)—R61, where m and R61 are defined above. WhereX50 is an oxygen and R55 is not hydrogen, the formula represents an“ester”. Where X50 is an oxygen, and R55 is as first defined above, themoiety is referred to herein as a carboxyl group, and particularly whenR55 is a hydrogen, the formula represents a “carboxylic acid”. Where X50is an oxygen, and R56 is hydrogen, the formula represents a “formate”.In general, where the oxygen atom of the above formula is replaced bysulfur, the formula represents a “thiocarbonyl” group. Where X50 is asulfur and R55 or R56 is not hydrogen, the formula represents a“thioester.” Where X50 is a sulfur and R55 is hydrogen, the formularepresents a “thiocarboxylic acid.” Where X50 is a sulfur and R56 ishydrogen, the formula represents a “thioformate.” On the other hand,where X50 is a bond, and R55 is not hydrogen, the above formularepresents a “ketone” group. Where X50 is a bond, and R55 is hydrogen,the above formula represents an “aldehyde” group.

The terms “oxime” and “oxime ether” are art-recognized and refer tomoieties that may be represented by the general formula:

wherein R75 is hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryl,aralkyl, or —(CH₂)_(m)—R61. The moiety is an “oxime” when R is H; and itis an “oxime ether” when R is alkyl, cycloalkyl, alkenyl, alkynyl, aryl,aralkyl, or —(CH₂)_(m)—R61.

The terms “alkoxyl” or “alkoxy” are art recognized and include an alkylgroup, as defined above, having an oxygen radical attached thereto.Representative alkoxyl groups include methoxy, ethoxy, propyloxy,tert-butoxy and the like. An “ether” is two hydrocarbons covalentlylinked by an oxygen. Accordingly, the substituent of an alkyl thatrenders that alkyl an ether is or resembles an alkoxyl, such as may berepresented by one of —O-alkyl, —O-alkenyl, —O-alkynyl,—O—(CH₂)_(m)—R61, where m and R61 are described above.

The term “sulfonate” is art recognized and includes a moiety that may berepresented by the general formula:

in which R57 is an electron pair, hydrogen, alkyl, cycloalkyl, or aryl.

The term “sulfate” is art recognized and includes a moiety that may berepresented by the general formula:

in which R57 is as defined above.

The term “sulfonamido” is art recognized and includes a moiety that maybe represented by the general formula:

in which R50 and R56 are as defined above.

The term “sulfamoyl” is art-recognized and includes a moiety that may berepresented by the general formula:

in which R50 and R51 are as defined above.

The term “sulfonyl” is art recognized and includes a moiety that may berepresented by the general formula:

in which R58 is one of the following: hydrogen, alkyl, alkenyl, alkynyl,cycloalkyl, heterocyclyl, aryl or heteroaryl.

The term “sulfoxido” is art recognized and includes a moiety that may berepresented by the general formula:

in which R58 is defined above.

The term “phosphoryl” is art-recognized and may in general berepresented by the formula:

wherein Q50 represents S or O, and R59 represents hydrogen, a loweralkyl or an aryl. When used to substitute, e.g., an alkyl, thephosphoryl group of the phosphorylalkyl may be represented by thegeneral formulas:

wherein Q50 and R59, each independently, are defined above, and Q51represents O, S or N. When Q50 is S, the phosphoryl moiety is a“phosphorothioate”.

The term “phosphoramidite” is art recognized and includes moietiesrepresented by the general formulas:

wherein Q51, R50, R51 and R59 are as defined above.

The term “phosphonamidite” is art recognized and includes moietiesrepresented by the general formulas:

wherein Q51, R50, R51 and R59 are as defined above, and R60 represents alower alkyl or an aryl.

The term “selenoalkyl” is art-recognized and refers to an alkyl grouphaving a substituted seleno group attached thereto. Exemplary“selenoethers” which may be substituted on the alkyl are selected fromone of —Se-alkyl, —Se-alkenyl, —Se-alkynyl, and —Se—(CH₂)_(m)—R61, m andR61 being defined above.

The terms triflyl, tosyl, mesyl, and nonaflyl are art-recognized andrefer to trifluoromethanesulfonyl, p-toluenesulfonyl, methanesulfonyl,and nonafluorobutanesulfonyl groups, respectively. The terms triflate,tosylate, mesylate, and nonaflate are art-recognized and refer totrifluoromethanesulfonate ester, p-toluenesulfonate ester,methanesulfonate ester, and nonafluorobutanesulfonate ester functionalgroups and molecules that contain said groups, respectively.

The abbreviations Me, Et, Ph, Tf, Nf, Ts, and Ms represent methyl,ethyl, phenyl, trifluoromethanesulfonyl, nonafluorobutanesulfonyl,p-toluenesulfonyl and methanesulfonyl, respectively. A morecomprehensive list of the abbreviations utilized by organic chemists ofordinary skill in the art appears in the first issue of each volume ofthe Journal of Organic Chemistry; this list is typically presented in atable entitled Standard List of Abbreviations.

Certain compounds contained in compositions of the present invention mayexist in particular geometric or stereoisomeric forms. In addition,polymers of the present invention may also be optically active. Thepresent invention contemplates all such compounds, including cis- andtrans-isomers, R- and S-enantiomers, diastereomers, (D)-isomers,(L)-isomers, the racemic mixtures thereof, and other mixtures thereof,as falling within the scope of the invention. Additional asymmetriccarbon atoms may be present in a substituent such as an alkyl group. Allsuch isomers, as well as mixtures thereof, are intended to be includedin this invention.

If, for instance, a particular enantiomer of compound of the presentinvention is desired, it may be prepared by asymmetric synthesis, or byderivation with a chiral auxiliary, where the resulting diastereomericmixture is separated and the auxiliary group cleaved to provide the puredesired enantiomers. Alternatively, where the molecule contains a basicfunctional group, such as amino, or an acidic functional group, such ascarboxyl, diastereomeric salts are formed with an appropriateoptically-active acid or base, followed by resolution of thediastereomers thus formed by fractional crystallization orchromatographic means well known in the art, and subsequent recovery ofthe pure enantiomers.

It will be understood that “substitution” or “substituted with” includesthe implicit proviso that such substitution is in accordance withpermitted valence of the substituted atom and the substituent, and thatthe substitution results in a stable compound, e.g., which does notspontaneously undergo transformation such as by rearrangement,cyclization, elimination, or other reaction.

The term “substituted” is also contemplated to include all permissiblesubstituents of organic compounds. In a broad aspect, the permissiblesubstituents include acyclic and cyclic, branched and unbranched,carbocyclic and heterocyclic, aromatic and nonaromatic substituents oforganic compounds. Illustrative substituents include, for example, thosedescribed herein above. The permissible substituents may be one or moreand the same or different for appropriate organic compounds. Forpurposes of this invention, the heteroatoms, such as nitrogen may havehydrogen substituents and/or any permissible substituents of organiccompounds described herein which satisfy the valences of theheteroatoms. This invention is not intended to be limited in any mannerby the permissible substituents of organic compounds.

Analogous substitutions may be made to alkenyl and alkynyl groups toproduce, for example, aminoalkenyls, aminoalkynyls, amidoalkenyls,amidoalkynyls, iminoalkenyls, iminoalkynyls, thioalkenyls, thioalkynyls,carbonyl-substituted alkenyls or alkynyls.

The definition of each expression, e.g., alkyl, m, n, etc., when itoccurs more than once in any structure, is intended to be independent ofits definition elsewhere in the same structure unless otherwiseindicated expressly or by the context.

For purposes of the invention, the chemical elements are identified inaccordance with the Periodic Table of the Elements, CAS version,Handbook of Chemistry and Physics, 67th Ed., 1986-87, inside cover.

SULFONATE ANION-CONTAINING SALTS. One aspect of the invention relates toa salt represented by

wherein, independently for each occurrence,

W represents an ammonium cation, a phosphonium cation, a heterocycliccation, an alkali metal cation or an alkaline earth metal cation;

T represents N or P;

Y represents CH₂, CHF, CF₂ or Z—O—Z;

Z represents CH₂, CHF or CF₂;

R₁ represents hydrogen, alkyl, fluoroalkyl, cycloalkyl,heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl, alkynyl,aryl, heteroaryl, aralkyl, heteroaralkyl, or arylcycloalkyl; whereinsaid alkyl, fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl,cycloalkenyl, heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl,heteroaralkyl, or arylcycloalkyl may be substituted with 1 to 3substituents selected from the group consisting of halogen, azide,alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, alkoxyl, amino,nitro, sulfhydryl, imino, amido, phosphonate, phosphinate, carbonyl,carboxyl, silyl, ether, alkylthio, sulfonyl, sulfonamido, ketone,aldehyde, ester, heterocyclyl, aryl, heteroaryl, fluoroalkyl and cyano;

R₂ represents alkyl, fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl,cycloalkenyl, heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl,heteroaralkyl, or arylcycloalkyl; wherein said alkyl, fluoroalkyl,cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl,alkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl, or arylcycloalkyl maybe substituted with 1 to 3 substituents selected from the groupconsisting of halogen, azide, alkyl, aralkyl, alkenyl, alkynyl,cycloalkyl, hydroxyl, alkoxyl, amino, nitro, sulfhydryl, imino, amido,phosphonate, phosphinate, carbonyl, carboxyl, silyl, ether, alkylthio,sulfonyl, sulfonamido, ketone, aldehyde, ester, heterocyclyl, aryl,heteroaryl, fluoroalkyl and cyano;

R₃ represents hydrogen, alkyl, fluoroalkyl, cycloalkyl,heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl, alkynyl,aryl, heteroaryl, aralkyl, heteroaralkyl, arylcycloalkyl, bicyclic ring,tricyclic ring, bicyclic or tricyclic fused ring, —(CH₂)_(n)—R₈,—C(═O)OR₈, —C(═O)N(R₈)₂, —C(═O)SR₈, —C(═O)R₈, —C(═NR₈)R₈, —C(═S)R₈,—C(R₈)═C(R₈)₂, —C≡CR₈, —CH(R₈)₂, —C(R₈)₃, or —(CH₂)_(n)—NH₂;

R₈ represents independently for each occurrence —(CH₂)_(n)—CH₃,cycloalkyl, aryl, or heteroaryl;

m represents independently for each occurrence an integer in the range1-10 inclusive; and

n represents independently for each occurrence an integer in the range1-10 inclusive.

In certain embodiments, the invention relates to any of theaforementioned salts, wherein the salt is represented by

In certain embodiments, the invention relates to any of theaforementioned salts, wherein the salt is represented by

In certain embodiments, the invention relates to any of theaforementioned salts, wherein W is an ammonium, pyridinium, imidazolium,benzimidazolium, pyrazolium, benzpyrazolium, indazolium, thiazolium,benzthiazolium, oxazolium, benzoxazolium, isoxazolium, isothiazolium,imdazolidenium, guanidinium, quinuclidinium, triazolium, tetrazolium,quinolinium, isoquinolinium, piperidinium, pyrrolidinium, morpholinium,pyridazinium, pyrazinium, piperazinium, triazinium, azepinium, ordiazepinium.

In certain embodiments, the invention relates to any of theaforementioned salts, wherein W is

R₄ and R₅ represent independently for each occurrence alkyl,fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl,heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl,arylcycloalkyl, —(CH₂)_(n)—R₈, —C(R₈)═C(R₈)₂, —C≡CR₈, —CH(R₈)₂, or—C(R₈)₃; or R₄ and R₅ taken together with the nitrogen to which they areattached form a five-, six-, or seven-membered heterocyclic ring; R₆represents alkyl, fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl,cycloalkenyl, heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl,heteroaralkyl, arylcycloalkyl, —(CH₂)_(n)—R₈, —C(R₈)═C(R₈)₂, —C≡CR₈,—CH(R₈)₂, or —C(R₈)₃; and R₇ represents alkyl, fluoroalkyl, cycloalkyl,heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl, alkynyl,aryl, heteroaryl, aralkyl, heteroaralkyl, arylcycloalkyl, —(CH₂)_(n)—R₈,—C(R₈)═C(R₈)₂, —C≡CR₈, —CH(R₈)₂, or —C(R₈)₃.

In certain embodiments, the invention relates to any of theaforementioned salts, wherein T represents N.

In certain embodiments, the invention relates to any of theaforementioned salts, wherein Y represents CH₂, CHF or CF₂. In certainembodiments, the invention relates to any of the aforementioned salts,wherein Y represents CH₂. In certain embodiments, the invention relatesto any of the aforementioned salts, wherein Y represents CF₂. In certainembodiments, the invention relates to any of the aforementioned salts,wherein only one Y represents Z—O—Z. In certain embodiments, theinvention relates to any of the aforementioned salts, wherein only one Yrepresents Z—O—Z; and Z is CH₂. In certain embodiments, the inventionrelates to any of the aforementioned salts, wherein only one Yrepresents Z—O—Z; and Z is CF₂.

In certain embodiments, the invention relates to any of theaforementioned salts, wherein R₁ is hydrogen. In certain embodiments,the invention relates to any of the aforementioned salts, wherein R₁ isnot hydrogen. In certain embodiments, the invention relates to any ofthe aforementioned salts, wherein R₁ represents alkyl, fluoroalkyl,cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl,alkynyl, aryl, heteroaryl, aralkyl, or heteroaralkyl. In certainembodiments, the invention relates to any of the aforementioned salts,wherein R₁ is alkyl, aryl or aralkyl. In certain embodiments, theinvention relates to any of the aforementioned salts, wherein R₁ isalkyl. In certain embodiments, the invention relates to any of theaforementioned salts, wherein R₁ represents ethyl, n-hexyl,1,5-dimethylhexyl, 2-ethylhexyl, 2-heptyl, isopropyl, isobutyl, or2-hydroxyethyl.

In certain embodiments, the invention relates to any of theaforementioned salts, wherein R₂ is alkyl, aryl or aralkyl. In certainembodiments, the invention relates to any of the aforementioned salts,wherein R₂ is alkyl.

In certain embodiments, the invention relates to any of theaforementioned salts, wherein R₃ is hydrogen or alkyl.

In certain embodiments, the invention relates to any of theaforementioned salts, wherein R₄, R₅, R₆, and R₇ represent alkyl.

In certain embodiments, the invention relates to any of theaforementioned salts, wherein m is 2 or 3.

In certain embodiments, the invention relates to any of theaforementioned salts, wherein the salt is represented by

R₁ represents hydrogen, alkyl, fluoroalkyl, cycloalkyl,heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl, alkynyl,aryl, heteroaryl, aralkyl, or heteroaralkyl; R₂ represents alkyl,fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl,heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl, orheteroaralkyl; R₃ represents hydrogen, alkyl, fluoroalkyl, cycloalkyl,heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl, alkynyl,aryl, heteroaryl, aralkyl, heteroaralkyl, —(CH₂)_(n)—R₈, —C(R₈)═C(R₈)₂,—C≡CR₈, —CH(R₈)₂, or —C(R₈)₃; R₄, R₅, R₆, and R₇ represent independentlyfor each occurrence methyl, ethyl, or n-butyl; and R₈ representsindependently for each occurrence —(CH₂)_(n)—CH₃, cycloalkyl, aryl, orheteroaryl.

In certain embodiments, the invention relates to any of theaforementioned salts, wherein the salt is represented by

In certain embodiments, the invention relates to any of theaforementioned salts, wherein the salt is represented by

In certain embodiments, the invention relates to any of theaforementioned salts, wherein R₁ represents ethyl, n-hexyl,1,5-dimethylhexyl, 2-ethylhexyl, 2-heptyl, isopropyl, isobutyl, or2-hydroxyethyl; and R₃ represents H or methyl.

In certain embodiments, the invention relates to any of theaforementioned salts, wherein R₁ represents ethyl, n-hexyl,1,5-dimethylhexyl, 2-ethylhexyl, 2-heptyl, isopropyl, isobutyl, or2-hydroxyethyl; R₃ represents H or methyl; and R₄, R₅, R₆, and R₇represent independently for each occurrence methyl, ethyl, or n-butyl.

In certain embodiments, the invention relates to any of theaforementioned salts, wherein R₁ represents ethyl, n-hexyl,1,5-dimethylhexyl, 2-ethylhexyl, 2-heptyl, isopropyl, isobutyl, or2-hydroxyethyl; R₃ represents H or methyl; R₄, R₅, R₆, and R₇ representindependently for each occurrence methyl, ethyl, or n-butyl; and m is 2or 3.

In certain embodiments, the invention relates to any of theaforementioned salts, wherein R₁ represents alkyl, aryl or aralkyl; andR₃ represents H or methyl.

In certain embodiments, the invention relates to any of theaforementioned salts, wherein R₁ represents alkyl, aryl or aralkyl; R₃represents H or methyl; and R₄, R₅, R₆, and R₇ represent independentlyfor each occurrence methyl, ethyl, or n-butyl.

In certain embodiments, the invention relates to any of theaforementioned salts, wherein R₁ represents alkyl, aryl or aralkyl; R₃represents H or methyl; R₄, R₅, R₆, and R₇ represent independently foreach occurrence methyl, ethyl, or n-butyl; and m is 2 or 3.

Another aspect of the invention relates to the salts formed when thesalts described above are used to sequester a gas (as described below).In addition, the invention also encompases the resulting salts formedwhen the gas-containing salts are heated (as described below).

SULFONIC ACID-CONTAINING SALTS. One aspect of the invention relates to asalt represented by

wherein, independently for each occurrence,

A represents boron tetrafluoride, phosphorus tetrafluoride, phosphorushexafluoride, alkylsulfonate, fluoroalkylsulfonate, arylsulfonate,bis(alkylsulfonyl)amide, bis(fluoroalkylsulfonyl)amide,bis(arylsulfonyl)amide,(fluoroalkylsulfonyl)-(fluoroalkylcarbonyl)amide, halide, nitrate,nitrite, sulfate, hydrogensulfate, alkyl sulfate, aryl sulfate,carbonate, bicarbonate, carboxylate, phosphate, hydrogen phosphate,dihydrogen phosphate, hypochlorite,tris(perfluoroalkyl)trifluorophosphate anion, or an anionic site of acation-exchange resin;

T represents N or P;

Y represents CH₂, CHF, CF₂ or Z—O—Z;

Z represents CH₂, CHF or CF₂;

R₁ represents hydrogen, alkyl, fluoroalkyl, cycloalkyl,heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl, alkynyl,aryl, heteroaryl, aralkyl, heteroaralkyl, or arylcycloalkyl; whereinsaid alkyl, fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl,cycloalkenyl, heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl,heteroaralkyl, or arylcycloalkyl may be substituted with 1 to 3substituents selected from the group consisting of halogen, azide,alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, alkoxyl, amino,nitro, sulfhydryl, imino, amido, phosphonate, phosphinate, carbonyl,carboxyl, silyl, ether, alkylthio, sulfonyl, sulfonamido, ketone,aldehyde, ester, heterocyclyl, aryl, heteroaryl, fluoroalkyl and cyano;

R₂ represents alkyl, fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl,cycloalkenyl, heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl,heteroaralkyl, or arylcycloalkyl; wherein said alkyl, fluoroalkyl,cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl,alkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl, or arylcycloalkyl maybe substituted with 1 to 3 substituents selected from the groupconsisting of halogen, azide, alkyl, aralkyl, alkenyl, alkynyl,cycloalkyl, hydroxyl, alkoxyl, amino, nitro, sulfhydryl, imino, amido,phosphonate, phosphinate, carbonyl, carboxyl, silyl, ether, alkylthio,sulfonyl, sulfonamido, ketone, aldehyde, ester, heterocyclyl, aryl,heteroaryl, fluoroalkyl and cyano;

R₃ represents hydrogen, alkyl, fluoroalkyl, cycloalkyl,heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl, alkynyl,aryl, heteroaryl, aralkyl, heteroaralkyl, arylcycloalkyl, bicyclic ring,tricyclic ring, bicyclic or tricyclic fused ring, —(CH₂)_(n)—R₈,—C(═O)OR₈, —C(═O)N(R₈)₂, —C(═O)SR₈, —C(═O)R₈, —C(═NR₈)R₈, —C(═S)R₈,—C(R₈)═C(R₈)₂, —C≡CR₈, —CH(R₈)₂, —C(R₈)₃, or —(CH₂)_(n)—NH₂;

R₈ represents independently for each occurrence —(CH₂)_(n)—CH₃,cycloalkyl, aryl, or heteroaryl;

m represents independently for each occurrence an integer in the range1-10 inclusive; and

n represents independently for each occurrence an integer in the range1-10 inclusive.

In certain embodiments, the invention relates to any of theaforementioned salts, wherein the salt is represented by

In certain embodiments, the invention relates to any of theaforementioned salts, wherein the salt is represented by

In certain embodiments, the invention relates to any of theaforementioned salts, wherein A represents I⁻¹, Br⁻¹, Cl⁻¹, HSO₄ ⁻¹,CH₃SO₃ ⁻¹, NO₃ ⁻¹, ClO₃ ⁻¹, FSO₃ ⁻¹, CF₃SO₃ ⁻¹, (CF₃SO₂)₂N⁻¹,tris(perfluoroalkyl)-trifluorophosphate (FAP) anions, or atetrafluoroethylene-perfluoro-3,6-dioxa-4-methyl-7-octenesulfonic acidcopolymer (Naftion).

In certain embodiments, the invention relates to any of theaforementioned salts, wherein T represents N.

In certain embodiments, the invention relates to any of theaforementioned salts, wherein Y represents CH₂, CHF or CF₂. In certainembodiments, the invention relates to any of the aforementioned salts,wherein Y represents CH₂. In certain embodiments, the invention relatesto any of the aforementioned salts, wherein Y represents CF₂. In certainembodiments, the invention relates to any of the aforementioned salts,wherein only one Y represents Z—O—Z. In certain embodiments, theinvention relates to any of the aforementioned salts, wherein only one Yrepresents Z—O—Z; and Z is CH₂. In certain embodiments, the inventionrelates to any of the aforementioned salts, wherein only one Yrepresents Z—O—Z; and Z is CF₂.

In certain embodiments, the invention relates to any of theaforementioned salts, wherein R₁ is hydrogen. In certain embodiments,the invention relates to any of the aforementioned salts, wherein R¹ isnot hydrogen. In certain embodiments, the invention relates to any ofthe aforementioned salts, wherein R₁ is alkyl, aryl or aralkyl. Incertain embodiments, the invention relates to any of the aforementionedsalts, wherein R₁ is alkyl.

In certain embodiments, the invention relates to any of theaforementioned salts, wherein R₂ is alkyl, aryl or aralkyl. In certainembodiments, the invention relates to any of the aforementioned salts,wherein R₂ is alkyl.

In certain embodiments, the invention relates to any of theaforementioned salts, wherein R₃ is hydrogen or alkyl.

In certain embodiments, the invention relates to any of theaforementioned salts, wherein m is 2 or 3.

In certain embodiments, the invention relates to any of theaforementioned salts, wherein R₁ represents alkyl, fluoroalkyl,cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl,alkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl, —(CH₂)_(n)—R₈,—C(R₈)═C(R₈)₂, —C≡CR₈, —CH(R₈)₂, or —C(R₈)₃; and R₃ represents hydrogen,alkyl, fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl,heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl,—(CH₂)_(n)—R₈, —C(R₈)═C(R₈)₂, —C≡CR₈, —CH(R₈)₂, or —C(R₈)₃.

In certain embodiments, the invention relates to any of theaforementioned salts, wherein T represents N; R₁ represents alkyl,fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl,heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl,—(CH₂)_(n)—R₈, —C(R₈)═C(R₈)₂, —C≡CR₈, —CH(R₈)₂, or —C(R₈)₃; and R₃represents hydrogen, alkyl, fluoroalkyl, cycloalkyl, heterocycloalkyl,alkenyl, cycloalkenyl, heterocycloalkenyl, alkynyl, aryl, heteroaryl,aralkyl, heteroaralkyl, —(CH₂)_(n)—R₈, —C(R₈)═C(R₈)₂, —C≡CR₈, —CH(R₈)₂,or —C(R₈)₃.

In certain embodiments, the invention relates to any of theaforementioned salts, wherein the salt is represented by

A represents I⁻¹, Br⁻¹, Cl⁻¹, HSO₄ ⁻¹, CH₃SO₃ ⁻¹, NO₃ ⁻¹, ClO₃ ⁻¹, FSO₃⁻¹, CF₃SO₃ ⁻¹, (CF₃SO₂)₂N⁻¹, tris(perfluoroalkyl)-trifluorophosphate(FAP) anions, or atetrafluoroethylene-perfluoro-3,6-dioxa-4-methyl-7-octenesulfonic acidcopolymer (Naftion); R₁ represents hydrogen, alkyl, fluoroalkyl,cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl,alkynyl, aryl, heteroaryl, aralkyl, or heteroaralkyl; R₂ representsalkyl, fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl,heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl, orheteroaralkyl; R₃ represents hydrogen, alkyl, fluoroalkyl, cycloalkyl,heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl, alkynyl,aryl, heteroaryl, aralkyl, heteroaralkyl, —(CH₂)_(n)—R₈, —C(R₈)═C(R₈)₂,—C≡CR₈, —CH(R₈)₂, or —C(R₈)₃; and R₈ represents independently for eachoccurrence —(CH₂)_(n)—CH₃, cycloalkyl, aryl, or heteroaryl.

In certain embodiments, the invention relates to any of theaforementioned salts, wherein the salt is represented by

In certain embodiments, the invention relates to any of theaforementioned salts, wherein the salt is represented by

In certain embodiments, the invention relates to any of theaforementioned salts, wherein R₁ represents n-hexyl, 1,5-dimethylhexyl,2-ethylhexyl, 2-heptyl, isopropyl, isobutyl, or 2-hydroxyethyl; and R₃represents H or methyl.

In certain embodiments, the invention relates to any of theaforementioned salts, wherein R₁ represents n-hexyl, 1,5-dimethylhexyl,2-ethylhexyl, 2-heptyl, isopropyl, isobutyl, or 2-hydroxyethyl; R₃represents H or methyl; and R₄, R₅, R₆, and R₇ represent independentlyfor each occurrence methyl, ethyl, or n-butyl.

In certain embodiments, the invention relates to any of theaforementioned salts, wherein R₁ represents n-hexyl, 1,5-dimethylhexyl,2-ethylhexyl, 2-heptyl, isopropyl, isobutyl, or 2-hydroxyethyl; R₃represents H or methyl; R₄, R₅, R₆, and R₇ represent independently foreach occurrence methyl, ethyl, or n-butyl; and m is 2 or 3.

In certain embodiments, the invention relates to any of theaforementioned salts, wherein R₁ represents alkyl, aryl or aralkyl; andR₃ represents H or methyl.

In certain embodiments, the invention relates to any of theaforementioned salts, wherein R₁ represents alkyl, aryl or aralkyl; R₃represents H or methyl; and m is 2 or 3.

Another aspect of the invention relates to the salts formed when thesalts described above are used to sequester a gas (as described below).In addition, the invention also encompases the resulting salts formedwhen the gas-containing salts are heated (as described below).

ARYL- AND HETEROARYL-CONTAINING SALTS. One aspect of the inventionrelates to a salt represented by

wherein, independently for each occurrence,

W represents an ammonium cation, a phosphonium cation, a heterocycliccation, an alkali metal cation or an alkaline earth metal cation;

T represents N or P;

E represents —C(═O)— or —S(═O)₂—;

A represents an aryl or heteroaryl diradical;

R₁ represents alkyl, fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl,cycloalkenyl, heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl,heteroaralkyl, or arylcycloalkyl; wherein said alkyl, fluoroalkyl,cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl,alkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl, or arylcycloalkyl maybe substituted with 1 to 3 substituents selected from the groupconsisting of halogen, azide, alkyl, aralkyl, alkenyl, alkynyl,cycloalkyl, hydroxyl, alkoxyl, amino, nitro, sulfhydryl, imino, amido,phosphonate, phosphinate, carbonyl, carboxyl, silyl, ether, alkylthio,sulfonyl, sulfonamido, ketone, aldehyde, ester, heterocyclyl, aryl,heteroaryl, fluoroalkyl and cyano;

R₄ and R₅ represent independently for each occurrence alkyl,fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl,heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl,arylcycloalkyl, —(CH₂)_(n)—R₈, —C(R₈)═C(R₈)₂, —C≡CR₈, —CH(R₈)₂, or—C(R₈)₃; or R₄ and R₅ taken together with the nitrogen to which they areattached form a five-, six-, or seven-membered heterocyclic ring;

R₆ represents alkyl, fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl,cycloalkenyl, heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl,heteroaralkyl, arylcycloalkyl, (CH₂)_(n)—R₈, —C(R₈)═C(R₈)₂, —C≡CR₈,—CH(R₈)₂, or —C(R₈)₃;

R₇ represents alkyl, fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl,cycloalkenyl, heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl,heteroaralkyl, arylcycloalkyl, —(CH₂)_(n)—R₈, —C(R₈)═C(R₈)₂, —C≡CR₈,—CH(R₈)₂, or —C(R₈)₃;

R₈ represents independently for each occurrence —(CH₂)_(n)—CH₃,cycloalkyl, aryl, or heteroaryl;

m represents independently for each occurrence an integer in the range1-10 inclusive; and

n represents independently for each occurrence an integer in the range1-10 inclusive.

In certain embodiments, the invention relates to any of theaforementioned salts, wherein W is an ammonium, pyridinium, imidazolium,benzimidazolium, pyrazolium, benzpyrazolium, indazolium, thiazolium,benzthiazolium, oxazolium, benzoxazolium, isoxazolium, isothiazolium,imdazolidenium, guanidinium, quinuclidinium, triazolium, tetrazolium,quinolinium, isoquinolinium, piperidinium, pyrrolidinium, morpholinium,pyridazinium, pyrazinium, piperazinium, triazinium, azepinium, ordiazepinium.

In certain embodiments, the invention relates to any of theaforementioned salts, wherein W is

R₄ and R₅ represent independently for each occurrence alkyl,fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl,heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl,arylcycloalkyl, —(CH₂)_(n)—R₈, —C(R₈)═C(R₈)₂, —C≡CR₈, —CH(R₈)₂, or—C(R₈)₃; or R₄ and R₅ taken together with the nitrogen to which they areattached form a five-, six-, or seven-membered heterocyclic ring; R₆represents alkyl, fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl,cycloalkenyl, heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl,heteroaralkyl, arylcycloalkyl, —(CH₂)_(n)—R₈, —C(R₈)═C(R₈)₂, —C≡CR₈,—CH(R₈)₂, or —C(R₈)₃; and R₇ represents alkyl, fluoroalkyl, cycloalkyl,heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl, alkynyl,aryl, heteroaryl, aralkyl, heteroaralkyl, arylcycloalkyl, —(CH₂)_(n)—R₈,—C(R₈)═C(R₈)₂, —C≡CR₈, —CH(R₈)₂, or —C(R₈)₃.

In certain embodiments, the invention relates to any of theaforementioned salts, wherein T represents N.

In certain embodiments, the invention relates to any of theaforementioned salts, wherein E represents —C(═O)—. In certainembodiments, the invention relates to any of the aforementioned salts,wherein E represents —S(═O)₂—.

In certain embodiments, the invention relates to any of theaforementioned salts, wherein R₁ is alkyl, aryl or aralkyl. In certainembodiments, the invention relates to any of the aforementioned salts,wherein R₁ is alkyl.

In certain embodiments, the invention relates to any of theaforementioned salts, wherein R₃ is hydrogen or alkyl.

In certain embodiments, the invention relates to any of theaforementioned salts, wherein R₄, R₅, R₆, and R₇ is alkyl.

In certain embodiments, the invention relates to any of theaforementioned salts, wherein A is an aryl diradical. In certainembodiments, the invention relates to any of the aforementioned salts,wherein A is an benzene diradical.

In certain embodiments, the invention relates to any of theaforementioned salts, wherein T represents N; R₁ represents alkyl,fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl,heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl,—CH₂CH(OH)—R₈, —(CH₂)_(n)—R₈, —C(R₈)═C(R₈)₂, —C≡CR₈, —CH(R₈)₂, or—C(R₈)₃; and A is an aryl diradical.

In certain embodiments, the invention relates to any of theaforementioned salts, wherein T represents N; R₁ represents alkyl,fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl,heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl,—CH₂CH(OH)—R₈, —(CH₂)_(n)—R₈, —C(R₈)═C(R₈)₂, —C≡CR₈, —CH(R₈)₂, or—C(R₈)₃; A is an aryl diradical; and R₄, R₅, R₆, and R₇ representindependently for each occurrence methyl, ethyl, or n-butyl.

In certain embodiments, the invention relates to any of theaforementioned salts, wherein R₁ represents alkyl, fluoroalkyl,cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl,alkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl, —CH₂CH(OH)—R₈,—(CH₂)_(n)—R₈, —C(R₈)═C(R₈)₂, —C≡CR₈, —CH(R₈)₂, or —C(R₈)₃; and A is anaryl diradical.

In certain embodiments, the invention relates to any of theaforementioned salts, wherein R₁ represents alkyl, fluoroalkyl,cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl,alkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl, —CH₂CH(OH)—R₈,—(CH₂)_(n)—R₈, —C(R₈)═C(R₈)₂, —C≡CR₈, —CH(R₈)₂, or —C(R₈)₃; A is an aryldiradical; and R₄, R₅, R₆, and R₇ represent independently for eachoccurrence methyl, ethyl, or n-butyl.

In certain embodiments, the invention relates to any of theaforementioned salts, wherein R₄, R₅, R₆, and R₇ represent independentlyfor each occurrence methyl, ethyl, or n-butyl.

In certain embodiments, the invention relates to any of theaforementioned salts, wherein the salt is represented by

R₁ represents alkyl, fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl,cycloalkenyl, heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl,heteroaralkyl or —CH₂CH(OH)—R₈ or —CH₂CHN(R₈)₂, R₄, R₅, R₆, and R₇represent independently for each occurrence methyl, ethyl, or n-butyl;and R₈ represents alkyl, aryl or aralkyl.

In certain embodiments, the invention relates to any of theaforementioned salts, wherein R₁ represents alkyl, aryl or aralkyl. Incertain embodiments, the invention relates to any of the aforementionedsalts, wherein R₁ represents —CH₂CH(OH)—R₈ or —CH₂CHN(R₈)₂. In certainembodiments, the invention relates to any of the aforementioned salts,wherein R₁ represents alkyl, aryl or aralkyl; and R₄, R₅, R₆, and R₇represent independently for each occurrence methyl, ethyl, or n-butyl.

Another aspect of the invention relates to a salt represented by

wherein, independently for each occurrence,

A represents boron tetrafluoride, phosphorus tetrafluoride, phosphorushexafluoride, alkylsulfonate, fluoroalkylsulfonate, arylsulfonate,bis(alkylsulfonyl)amide, bis(fluoroalkylsulfonyl)amide,bis(arylsulfonyl)amide,(fluoroalkylsulfonyl)-(fluoroalkylcarbonyl)amide, halide, nitrate,nitrite, sulfate, hydrogensulfate, alkyl sulfate, aryl sulfate,carbonate, bicarbonate, carboxylate, phosphate, hydrogen phosphate,dihydrogen phosphate, hypochlorite,tris(perfluoroalkyl)trifluorophosphate anion, or an anionic site of acation-exchange resin;

T represents N or P;

E represents —C(═O)— or —S(═O)₂—;

Z represents an aryl or heteroaryl diradical;

R₁ represents alkyl, fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl,cycloalkenyl, heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl,heteroaralkyl, or arylcycloalkyl; wherein said alkyl, fluoroalkyl,cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl,alkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl, or arylcycloalkyl maybe substituted with 1 to 3 substituents selected from the groupconsisting of halogen, azide, alkyl, aralkyl, alkenyl, alkynyl,cycloalkyl, hydroxyl, alkoxyl, amino, nitro, sulfhydryl, imino, amido,phosphonate, phosphinate, carbonyl, carboxyl, silyl, ether, alkylthio,sulfonyl, sulfonamido, ketone, aldehyde, ester, heterocyclyl, aryl,heteroaryl, fluoroalkyl and cyano;

R₈ represents independently for each occurrence —(CH₂)_(n)—CH₃,cycloalkyl, aryl, or heteroaryl;

m represents independently for each occurrence an integer in the range1-10 inclusive; and

n represents independently for each occurrence an integer in the range1-10 inclusive.

In certain embodiments, the invention relates to any of theaforementioned salts, wherein A represents I⁻¹, Br⁻¹, Cl⁻¹, HSO₄ ⁻¹,CH₃SO₃ ⁻¹, NO₃ ⁻¹, ClO₃ ⁻¹, FSO₃ ⁻¹, CF₃SO₃ ⁻¹, (CF₃SO₂)₂N⁻¹,tris(perfluoroalkyl)-trifluorophosphate (FAP) anions, or atetrafluoroethylene-perfluoro-3,6-dioxa-4-methyl-7-octenesulfonic acidcopolymer (Naftion).

In certain embodiments, the invention relates to any of theaforementioned salts, wherein T represents N.

In certain embodiments, the invention relates to any of theaforementioned salts, wherein E represents —C(═O)—. In certainembodiments, the invention relates to any of the aforementioned salts,wherein E represents —S(═O)₂—.

In certain embodiments, the invention relates to any of theaforementioned salts, wherein R₁ is alkyl, aryl or aralkyl. In certainembodiments, the invention relates to any of the aforementioned salts,wherein R₁ is alkyl.

In certain embodiments, the invention relates to any of theaforementioned salts, wherein R₃ is hydrogen or alkyl.

In certain embodiments, the invention relates to any of theaforementioned salts, wherein Z is an aryl diradical. In certainembodiments, the invention relates to any of the aforementioned salts,wherein Z is an benzene diradical.

In certain embodiments, the invention relates to any of theaforementioned salts, wherein R₁ represents alkyl, fluoroalkyl,cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl,alkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl, —CH₂CH(OH)—R₈,—(CH₂)_(n)—R₈, —C(R₈)═C(R₈)₂, —C≡CR₈, —CH(R₈)₂, or —C(R₈)₃; and Z is anaryl diradical.

In certain embodiments, the invention relates to any of theaforementioned salts, wherein T represents N; R₁ represents alkyl,fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl,heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl,—CH₂CH(OH)—R₈, —(CH₂)_(n)—R₈, —C(R₈)═C(R₈)₂, —C≡CR₈, —CH(R₈)₂, or—C(R₈)₃; and Z is an aryl diradical.

In certain embodiments, the invention relates to any of theaforementioned salts, wherein the salt is represented by

R₁ represents alkyl, fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl,cycloalkenyl, heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl,heteroaralkyl —CH₂CH(OH)—R₈ or —CH₂CHN(R₈)₂; and R₈ represents alkyl,aryl or aralkyl.

In certain embodiments, the invention relates to any of theaforementioned salts, wherein R₁ represents alkyl, aryl or aralkyl. Incertain embodiments, the invention relates to any of the aforementionedsalts, wherein R₁ represents —CH₂CH(OH)—R₈ or —CH₂CHN(R₈)₂. In certainembodiments, the invention relates to any of the aforementioned salts,wherein R₁ represents alkyl, aryl or aralkyl.

Another aspect of the invention relates to the salts formed when thesalts described above are used to sequester a gas (as described below).In addition, the invention also encompases the resulting salts formedwhen the gas-containing salts are heated (as described below).

METHODS OF SEQUESTERING A GAS. One aspect of the invention relates tosequestering a gas by contacting the gas with an ionic liquid. Incertain embodiments, one of the components in the ionic liquid comprisesa nucleophic moiety which can react with the gas to covalently bind thegas to one of the components of the ionic liquid, thereby sequesteringit.

In certain embodiments, the invention relates to a method ofsequestering a gas, comprising contacting the gas with a saltrepresented by any of the aforementioned salts.

In certain embodiments, the invention relates to the aforementionedmethod, wherein the salt is sulfonate anion-containing salt (asdescribed above).

In certain embodiments, the invention relates to the aforementionedmethod, wherein the salt is sulfonic acid-containing salt (as describedabove).

In certain embodiments, the invention relates to the aforementionedmethod, wherein the salt is aryl- or heteroaryl-containing salt (asdescribed above).

In certain embodiments, the invention relates to the aforementionedmethod, wherein the gas is CO₂, CS₂, SO₂ or NO₂.

In certain embodiments, the invention relates to the aforementionedmethod, wherein the gas is CO₂.

METHOD OF RELEASING A GAS. One aspect of the invention relates toreleasing a gas by heating a salt which had previously been used tosequested a gas (see above). In certain embodiments, a covalent bondlinks the gas to the salt. In other embodiments, a noncovalentassociation links the gas to the salt. By heating a compositioncomprising a salt to which a gas is bound covalently or associatednoncovalently, the gas can be released.

In certain embodiments, the invention relates to a method of releasing agas, comprising the step of heating a composition comprising a gasdissolved in a salt; wherein the salt is represented by any of theaforementioned salts.

In certain embodiments, the invention relates to the aforementionedmethod, wherein the salt is sulfonate anion-containing salt (asdescribed above).

In certain embodiments, the invention relates to the aforementionedmethod, wherein the salt is sulfonic acid-containing salt (as describedabove).

In certain embodiments, the invention relates to the aforementionedmethod, wherein the salt is aryl- or heteroaryl-containing salt (asdescribed above).

In certain embodiments, the invention relates to the aforementionedmethod, wherein the gas is CO₂, CS₂, SO₂ or NO₂.

In certain embodiments, the invention relates to the aforementionedmethod, wherein the gas is CO₂.

In certain embodiments, the invention relates to a method of releasing agas, comprising the step of heating a salt; wherein the salt isrepresented by

wherein, independently for each occurrence,

X represents —CO₂ ⁻¹, —CS₂ ⁻¹, —SO₂ ⁻¹ or —NO₂ ⁻¹;

W represents an ammonium cation, a phosphonium cation, a heterocycliccation, an alkali metal cation or an alkaline earth metal cation;

T represents N or P;

Y represents CH₂, CHF, CF₂ or Z—O—Z;

Z represents CH₂, CHF or CF₂;

R₁ represents hydrogen, alkyl, fluoroalkyl, cycloalkyl,heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl, alkynyl,aryl, heteroaryl, aralkyl, heteroaralkyl, or arylcycloalkyl; whereinsaid alkyl, fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl,cycloalkenyl, heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl,heteroaralkyl, or arylcycloalkyl may be substituted with 1 to 3substituents selected from the group consisting of halogen, azide,alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, alkoxyl, amino,nitro, sulfhydryl, imino, amido, phosphonate, phosphinate, carbonyl,carboxyl, silyl, ether, alkylthio, sulfonyl, sulfonamido, ketone,aldehyde, ester, heterocyclyl, aryl, heteroaryl, fluoroalkyl and cyano;

R₂ represents alkyl, fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl,cycloalkenyl, heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl,heteroaralkyl, or arylcycloalkyl; wherein said alkyl, fluoroalkyl,cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl,alkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl, or arylcycloalkyl maybe substituted with 1 to 3 substituents selected from the groupconsisting of halogen, azide, alkyl, aralkyl, alkenyl, alkynyl,cycloalkyl, hydroxyl, alkoxyl, amino, nitro, sulfhydryl, imino, amido,phosphonate, phosphinate, carbonyl, carboxyl, silyl, ether, alkylthio,sulfonyl, sulfonamido, ketone, aldehyde, ester, heterocyclyl, aryl,heteroaryl, fluoroalkyl and cyano;

R₃ represents hydrogen, alkyl, fluoroalkyl, cycloalkyl,heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl, alkynyl,aryl, heteroaryl, aralkyl, heteroaralkyl, arylcycloalkyl, bicyclic ring,tricyclic ring, bicyclic or tricyclic fused ring, —(CH₂)_(n)—R₈,—C(═O)OR₈, —C(═O)N(R₈)₂, —C(═O)SR₈, —C(═O)R₈, —C(═NR₈)R₈, —C(═S)R₈,—C(R₈)═C(R₈)₂, —C≡CR₈, —CH(R₈)₂, —C(R₈)₃, or —(CH₂)_(n)—NH₂;

R₈ represents independently for each occurrence —(CH₂)_(n)—CH₃,cycloalkyl, aryl, or heteroaryl;

m represents independently for each occurrence an integer in the range1-10 inclusive; and

n represents independently for each occurrence an integer in the range1-10 inclusive.

In certain embodiments, the invention relates to any of theaforementioned methods, wherein the salt is represented by

In certain embodiments, the invention relates to any of theaforementioned methods, wherein the salt is represented by

In certain embodiments, the invention relates to any of theaforementioned methods, wherein X is —CO₂ ⁻¹.

In certain embodiments, the invention relates to any of theaforementioned methods, wherein W is an ammonium, pyridinium,imidazolium, benzimidazolium, pyrazolium, benzpyrazolium, indazolium,thiazolium, benzthiazolium, oxazolium, benzoxazolium, isoxazolium,isothiazolium, imdazolidenium, guanidinium, quinuclidinium, triazolium,tetrazolium, quinolinium, isoquinolinium, piperidinium, pyrrolidinium,morpholinium, pyridazinium, pyrazinium, piperazinium, triazinium,azepinium, or diazepinium.

In certain embodiments, the invention relates to any of theaforementioned methods, wherein W is

R₄ and R₅ represent independently for each occurrence alkyl,fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl,heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl,arylcycloalkyl, —(CH₂)_(n)—R₈, —C(R₈)═C(R₈)₂, —C≡CR₈, —CH(R₈)₂, or—C(R₈)₃; or R₄ and R₅ taken together with the nitrogen to which they areattached form a five-, six-, or seven-membered heterocyclic ring; R₆represents alkyl, fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl,cycloalkenyl, heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl,heteroaralkyl, arylcycloalkyl, —(CH₂)_(n)—R₈, —C(R₈)═C(R₈)₂, —C≡CR₈,—CH(R₈)₂, or —C(R₈)₃; and R₇ represents alkyl, fluoroalkyl, cycloalkyl,heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl, alkynyl,aryl, heteroaryl, aralkyl, heteroaralkyl, arylcycloalkyl, —(CH₂)_(n)—R₈,—C(R₈)═C(R₈)₂, —C≡CR₈, —CH(R₈)₂, or —C(R₈)₃.

In certain embodiments, the invention relates to any of theaforementioned methods, wherein T represents N.

In certain embodiments, the invention relates to any of theaforementioned methods, wherein Y represents CH₂, CHF or CF₂. In certainembodiments, the invention relates to any of the aforementioned methods,wherein Y represents CH₂. In certain embodiments, the invention relatesto any of the aforementioned methods, wherein Y represents CF₂. Incertain embodiments, the invention relates to any of the aforementionedmethods, wherein only one Y represents Z—O—Z. In certain embodiments,the invention relates to any of the aforementioned methods, wherein onlyone Y represents Z—O—Z; and Z is CH₂. In certain embodiments, theinvention relates to any of the aforementioned methods, wherein only oneY represents Z—O—Z; and Z is CF₂.

In certain embodiments, the invention relates to any of theaforementioned methods, wherein R₁ is hydrogen. In certain embodiments,the invention relates to any of the aforementioned methods, wherein R₁is not hydrogen. In certain embodiments, the invention relates to any ofthe aforementioned methods, wherein R₁ represents alkyl, fluoroalkyl,cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl,alkynyl, aryl, heteroaryl, aralkyl, or heteroaralkyl. In certainembodiments, the invention relates to any of the aforementioned methods,wherein R₁ is alkyl, aryl or aralkyl. In certain embodiments, theinvention relates to any of the aforementioned methods, wherein R₁ isalkyl. In certain embodiments, the invention relates to any of theaforementioned methods, wherein R₁ represents ethyl, n-hexyl,1,5-dimethylhexyl, 2-ethylhexyl, 2-heptyl, isopropyl, isobutyl, or2-hydroxyethyl.

In certain embodiments, the invention relates to any of theaforementioned methods, wherein R₂ is alkyl, aryl or aralkyl. In certainembodiments, the invention relates to any of the aforementioned methods,wherein R₂ is alkyl.

In certain embodiments, the invention relates to any of theaforementioned methods, wherein R₃ is hydrogen or alkyl.

In certain embodiments, the invention relates to any of theaforementioned methods, wherein R₄, R₅, R₆, and R₇ represent alkyl.

In certain embodiments, the invention relates to any of theaforementioned methods, wherein m is 2 or 3.

In certain embodiments, the invention relates to any of theaforementioned methods, wherein the salt is represented by

R₁ represents hydrogen, alkyl, fluoroalkyl, cycloalkyl,heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl, alkynyl,aryl, heteroaryl, aralkyl, or heteroaralkyl; R₂ represents alkyl,fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl,heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl, orheteroaralkyl; R₃ represents hydrogen, alkyl, fluoroalkyl, cycloalkyl,heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl, alkynyl,aryl, heteroaryl, aralkyl, heteroaralkyl, —(CH₂)_(n)—R₈, —C(R₈)═C(R₈)₂,—C≡CR₈, —CH(R₈)₂, or —C(R₈)₃; R₄, R₅, R₆, and R₇ represent independentlyfor each occurrence methyl, ethyl, or n-butyl; and R₈ representsindependently for each occurrence —(CH₂)_(n)—CH₃, cycloalkyl, aryl, orheteroaryl.

In certain embodiments, the invention relates to any of theaforementioned methods, wherein the salt is represented by

In certain embodiments, the invention relates to any of theaforementioned methods, wherein the salt is represented by

In certain embodiments, the invention relates to any of theaforementioned methods, wherein R₁ represents ethyl, n-hexyl,1,5-dimethylhexyl, 2-ethylhexyl, 2-heptyl, isopropyl, isobutyl, or2-hydroxyethyl; and R₃ represents H or methyl.

In certain embodiments, the invention relates to any of theaforementioned methods, wherein R₁ represents ethyl, n-hexyl,1,5-dimethylhexyl, 2-ethylhexyl, 2-heptyl, isopropyl, isobutyl, or2-hydroxyethyl; R₃ represents H or methyl; and R₄, R₅, R₆, and R₇represent independently for each occurrence methyl, ethyl, or n-butyl.

In certain embodiments, the invention relates to any of theaforementioned methods, wherein R₁ represents ethyl, n-hexyl,1,5-dimethylhexyl, 2-ethylhexyl, 2-heptyl, isopropyl, isobutyl, or2-hydroxyethyl; R₃ represents H or methyl; R₄, R₅, R₆, and R₇ representindependently for each occurrence methyl, ethyl, or n-butyl; and m is 2or 3.

In certain embodiments, the invention relates to any of theaforementioned methods, wherein R₁ represents alkyl, aryl or aralkyl;and R₃ represents H or methyl.

In certain embodiments, the invention relates to any of theaforementioned methods, wherein R₁ represents alkyl, aryl or aralkyl; R₃represents H or methyl; and R₄, R₅, R₆, and R₇ represent independentlyfor each occurrence methyl, ethyl, or n-butyl.

In certain embodiments, the invention relates to any of theaforementioned methods, wherein R₁ represents alkyl, aryl or aralkyl; R₃represents H or methyl; R₄, R₅, R₆, and R₇ represent independently foreach occurrence methyl, ethyl, or n-butyl; and m is 2 or 3.

In certain embodiments, the invention relates to a method of releasing agas, comprising the step of heating a salt; wherein the salt isrepresented by

wherein, independently for each occurrence,

X represents —CO₂ ⁻¹, —CS₂ ⁻¹, —SO₂ ⁻¹ or —NO₂ ⁻¹;

A represents boron tetrafluoride, phosphorus tetrafluoride, phosphorushexafluoride, alkylsulfonate, fluoroalkylsulfonate, arylsulfonate,bis(alkylsulfonyl)amide, bis(fluoroalkylsulfonyl)amide,bis(arylsulfonyl)amide,(fluoroalkylsulfonyl)-(fluoroalkylcarbonyl)amide, halide, nitrate,nitrite, sulfate, hydrogensulfate, alkyl sulfate, aryl sulfate,carbonate, bicarbonate, carboxylate, phosphate, hydrogen phosphate,dihydrogen phosphate, hypochlorite,tris(perfluoroalkyl)trifluorophosphate anion, or an anionic site of acation-exchange resin;

T represents N or P;

Y represents CH₂, CHF, CF₂ or Z—O—Z;

Z represents CH₂, CHF or CF₂;

R₁ represents hydrogen, alkyl, fluoroalkyl, cycloalkyl,heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl, alkynyl,aryl, heteroaryl, aralkyl, heteroaralkyl, or arylcycloalkyl; whereinsaid alkyl, fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl,cycloalkenyl, heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl,heteroaralkyl, or arylcycloalkyl may be substituted with 1 to 3substituents selected from the group consisting of halogen, azide,alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, alkoxyl, amino,nitro, sulfhydryl, imino, amido, phosphonate, phosphinate, carbonyl,carboxyl, silyl, ether, alkylthio, sulfonyl, sulfonamido, ketone,aldehyde, ester, heterocyclyl, aryl, heteroaryl, fluoroalkyl and cyano;

R₂ represents alkyl, fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl,cycloalkenyl, heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl,heteroaralkyl, or arylcycloalkyl; wherein said alkyl, fluoroalkyl,cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl,alkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl, or arylcycloalkyl maybe substituted with 1 to 3 substituents selected from the groupconsisting of halogen, azide, alkyl, aralkyl, alkenyl, alkynyl,cycloalkyl, hydroxyl, alkoxyl, amino, nitro, sulfhydryl, imino, amido,phosphonate, phosphinate, carbonyl, carboxyl, silyl, ether, alkylthio,sulfonyl, sulfonamido, ketone, aldehyde, ester, heterocyclyl, aryl,heteroaryl, fluoroalkyl and cyano;

R₃ represents hydrogen, alkyl, fluoroalkyl, cycloalkyl,heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl, alkynyl,aryl, heteroaryl, aralkyl, heteroaralkyl, arylcycloalkyl, bicyclic ring,tricyclic ring, bicyclic or tricyclic fused ring, —(CH₂)_(n)—R₈,—C(═O)OR₈, —C(═O)N(R₈)₂, —C(═O)SR₈, —C(═O)R₈, —C(═NR₈)R₈, —C(═S)R₈,—C(R₈)═C(R₈)₂, —C≡CR₈, —CH(R₈)₂, —C(R₈)₃, or —(CH₂)_(n)—NH₂;

R₈ represents independently for each occurrence —(CH₂)_(n)—CH₃,cycloalkyl, aryl, or heteroaryl;

m represents independently for each occurrence an integer in the range1-10 inclusive; and

n represents independently for each occurrence an integer in the range1-10 inclusive.

In certain embodiments, the invention relates to any of theaforementioned methods, wherein X is —CO₂ ⁻¹.

In certain embodiments, the invention relates to any of theaforementioned methods, wherein the salt is represented by

In certain embodiments, the invention relates to any of theaforementioned methods, wherein the salt is represented by

In certain embodiments, the invention relates to any of theaforementioned methods, wherein A represents I⁻¹, Br⁻¹, Cl⁻¹, HSO₄ ⁻¹,CH₃SO₃ ⁻¹, NO₃ ⁻¹, ClO₃ ⁻¹, FSO₃ ⁻¹, CF₃SO₃ ⁻¹, (CF₃SO₂)₂N⁻¹,tris(perfluoroalkyl)-trifluorophosphate (FAP) anions, or atetrafluoroethylene-perfluoro-3,6-dioxa-4-methyl-7-octenesulfonic acidcopolymer (Naftion).

In certain embodiments, the invention relates to any of theaforementioned methods, wherein T represents N.

In certain embodiments, the invention relates to any of theaforementioned methods, wherein Y represents CH₂, CHF or CF₂. In certainembodiments, the invention relates to any of the aforementioned methods,wherein Y represents CH₂. In certain embodiments, the invention relatesto any of the aforementioned methods, wherein Y represents CF₂. Incertain embodiments, the invention relates to any of the aforementionedmethods, wherein only one Y represents Z—O—Z. In certain embodiments,the invention relates to any of the aforementioned methods, wherein onlyone Y represents Z—O—Z; and Z is CH₂. In certain embodiments, theinvention relates to any of the aforementioned methods, wherein only oneY represents Z—O—Z; and Z is CF₂.

In certain embodiments, the invention relates to any of theaforementioned methods, wherein R₁ is hydrogen. In certain embodiments,the invention relates to any of the aforementioned methods, wherein R¹is not hydrogen. In certain embodiments, the invention relates to any ofthe aforementioned methods, wherein R₁ is alkyl, aryl or aralkyl. Incertain embodiments, the invention relates to any of the aforementionedmethods, wherein R₁ is alkyl.

In certain embodiments, the invention relates to any of theaforementioned methods, wherein R₂ is alkyl, aryl or aralkyl. In certainembodiments, the invention relates to any of the aforementioned methods,wherein R₂ is alkyl.

In certain embodiments, the invention relates to any of theaforementioned methods, wherein R₃ is hydrogen or alkyl.

In certain embodiments, the invention relates to any of theaforementioned methods, wherein m is 2 or 3.

In certain embodiments, the invention relates to any of theaforementioned methods, wherein R₁ represents alkyl, fluoroalkyl,cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl,alkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl, —(CH₂)_(n)—R₈,—C(R₈)═C(R₈)₂, —C≡CR₈, —CH(R₈)₂, or —C(R₈)₃; and R₃ represents hydrogen,alkyl, fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl,heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl,—(CH₂)_(n)—R₈, —C(R₈)═C(R₈)₂, —C≡CR₈, —CH(R₈)₂, or —C(R₈)₃.

In certain embodiments, the invention relates to any of theaforementioned methods, wherein T represents N; R₁ represents alkyl,fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl,heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl,—(CH₂)_(n)—R₈, —C(R₈)═C(R₈)₂, —C≡CR₈, —CH(R₈)₂, or —C(R₈)₃; and R₃represents hydrogen, alkyl, fluoroalkyl, cycloalkyl, heterocycloalkyl,alkenyl, cycloalkenyl, heterocycloalkenyl, alkynyl, aryl, heteroaryl,aralkyl, heteroaralkyl, —(CH₂)_(n)—R₈, —C(R₈)═C(R₈)₂, —C≡CR₈, —CH(R₈)₂,or —C(R₈)₃.

In certain embodiments, the invention relates to any of theaforementioned methods, wherein the salt is represented by

A represents I⁻¹, Br⁻¹, Cl⁻¹, HSO₄ ⁻¹, CH₃SO₃ ⁻¹, NO₃ ⁻¹, ClO₃ ⁻¹, FSO₃⁻¹, CF₃SO₃ ⁻¹, (CF₃SO₂)₂N⁻¹, tris(perfluoroalkyl)-trifluorophosphate(FAP) anions, or atetrafluoroethylene-perfluoro-3,6-dioxa-4-methyl-7-octenesulfonic acidcopolymer (Naftion); R₁ represents hydrogen, alkyl, fluoroalkyl,cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl,alkynyl, aryl, heteroaryl, aralkyl, or heteroaralkyl; R₂ representsalkyl, fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl,heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl, orheteroaralkyl; R₃ represents hydrogen, alkyl, fluoroalkyl, cycloalkyl,heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl, alkynyl,aryl, heteroaryl, aralkyl, heteroaralkyl, —(CH₂)_(n)—R₈, —C(R₈)═C(R₈)₂,—C≡CR₈, —CH(R₈)₂, or —C(R₈)₃; and R₈ represents independently for eachoccurrence —(CH₂)_(n)—CH₃, cycloalkyl, aryl, or heteroaryl.

In certain embodiments, the invention relates to any of theaforementioned methods, wherein the salt is represented by

In certain embodiments, the invention relates to any of theaforementioned methods, wherein the salt is represented by

In certain embodiments, the invention relates to any of theaforementioned methods, wherein R₁ represents n-hexyl,1,5-dimethylhexyl, 2-ethylhexyl, 2-heptyl, isopropyl, isobutyl, or2-hydroxyethyl; and R₃ represents H or methyl.

In certain embodiments, the invention relates to any of theaforementioned methods, wherein R₁ represents n-hexyl,1,5-dimethylhexyl, 2-ethylhexyl, 2-heptyl, isopropyl, isobutyl, or2-hydroxyethyl; R₃ represents H or methyl; and m is 2 or 3.

In certain embodiments, the invention relates to any of theaforementioned methods, wherein R₁ represents alkyl, aryl or aralkyl;and R₃ represents H or methyl.

In certain embodiments, the invention relates to any of theaforementioned methods, wherein R₁ represents alkyl, aryl or aralkyl; R₃represents H or methyl; and m is 2 or 3.

In certain embodiments, the invention relates to a method of releasing agas, comprising the step of heating a salt; wherein the salt isrepresented by

wherein, independently for each occurrence,

X represents —CO₂ ⁻¹, —CS₂ ⁻¹, —SO₂ ⁻¹ or —NO₂ ⁻¹;

W represents an ammonium cation, a phosphonium cation, a heterocycliccation, an alkali metal cation or an alkaline earth metal cation;

T represents N or P;

E represents —C(═O)— or —S(═O)₂—;

A represents an aryl or heteroaryl diradical;

R₁ represents alkyl, fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl,cycloalkenyl, heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl,heteroaralkyl, or arylcycloalkyl; wherein said alkyl, fluoroalkyl,cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl,alkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl, or arylcycloalkyl maybe substituted with 1 to 3 substituents selected from the groupconsisting of halogen, azide, alkyl, aralkyl, alkenyl, alkynyl,cycloalkyl, hydroxyl, alkoxyl, amino, nitro, sulfhydryl, imino, amido,phosphonate, phosphinate, carbonyl, carboxyl, silyl, ether, alkylthio,sulfonyl, sulfonamido, ketone, aldehyde, ester, heterocyclyl, aryl,heteroaryl, fluoroalkyl and cyano;

R₈ represents independently for each occurrence —(CH₂)_(n)—CH₃,cycloalkyl, aryl, or heteroaryl;

m represents independently for each occurrence an integer in the range1-10 inclusive; and

n represents independently for each occurrence an integer in the range1-10 inclusive.

In certain embodiments, the invention relates to any of theaforementioned methods, wherein X is —CO₂ ⁻¹.

In certain embodiments, the invention relates to any of theaforementioned methods, wherein W is an ammonium, pyridinium,imidazolium, benzimidazolium, pyrazolium, benzpyrazolium, indazolium,thiazolium, benzthiazolium, oxazolium, benzoxazolium, isoxazolium,isothiazolium, imdazolidenium, guanidinium, quinuclidinium, triazolium,tetrazolium, quinolinium, isoquinolinium, piperidinium, pyrrolidinium,morpholinium, pyridazinium, pyrazinium, piperazinium, triazinium,azepinium, or diazepinium.

In certain embodiments, the invention relates to any of theaforementioned methods, wherein W is

R₄ and R₅ represent independently for each occurrence alkyl,fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl,heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl,arylcycloalkyl, —(CH₂)_(n)—R₈, —C(R₈)═C(R₈)₂, —C≡CR₈, —CH(R₈)₂, or—C(R₈)₃; or R₄ and R₅ taken together with the nitrogen to which they areattached form a five-, six-, or seven-membered heterocyclic ring; R₆represents alkyl, fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl,cycloalkenyl, heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl,heteroaralkyl, arylcycloalkyl, —(CH₂)_(n)—R₈, —C(R₈)═C(R₈)₂, —C≡CR₈,—CH(R₈)₂, or —C(R₈)₃; and R₇ represents alkyl, fluoroalkyl, cycloalkyl,heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl, alkynyl,aryl, heteroaryl, aralkyl, heteroaralkyl, arylcycloalkyl, —(CH₂)_(n)—R₈,—C(R₈)═C(R₈)₂, —C≡CR₈, —CH(R₈)₂, or —C(R₈)₃.

In certain embodiments, the invention relates to any of theaforementioned methods, wherein T represents N.

In certain embodiments, the invention relates to any of theaforementioned methods, wherein E represents —C(═O)—. In certainembodiments, the invention relates to any of the aforementioned methods,wherein E represents —S(═O)₂—.

In certain embodiments, the invention relates to any of theaforementioned methods, wherein R₁ is alkyl, aryl or aralkyl. In certainembodiments, the invention relates to any of the aforementioned methods,wherein R₁ is alkyl.

In certain embodiments, the invention relates to any of theaforementioned methods, wherein R₃ is hydrogen or alkyl.

In certain embodiments, the invention relates to any of theaforementioned methods, wherein R₄, R₅, R₆, and R₇ is alkyl.

In certain embodiments, the invention relates to any of theaforementioned methods, wherein A is an aryl diradical. In certainembodiments, the invention relates to any of the aforementioned methods,wherein A is an benzene diradical.

In certain embodiments, the invention relates to any of theaforementioned methods, wherein T represents N; R₁ represents alkyl,fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl,heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl,—CH₂CH(OH)—R₈, —(CH₂)_(n)—R₈, —C(R₈)═C(R₈)₂, —C≡CR₈, —CH(R₈)₂, or—C(R₈)₃; and A is an aryl diradical.

In certain embodiments, the invention relates to any of theaforementioned methods, wherein T represents N; R₁ represents alkyl,fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl,heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl,—CH₂CH(OH)—R₈, —(CH₂)_(n)—R₈, —C(R₈)═C(R₈)₂, —C≡CR₈, —CH(R₈)₂, or—C(R₈)₃; A is an aryl diradical; and R₄, R₅, R₆, and R₇ representindependently for each occurrence methyl, ethyl, or n-butyl.

In certain embodiments, the invention relates to any of theaforementioned methods, wherein R₁ represents alkyl, fluoroalkyl,cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl,alkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl, —CH₂CH(OH)—R₈,—(CH₂)_(n)—R₈, —C(R₈)═C(R₈)₂, —C≡CR₈, —CH(R₈)₂, or —C(R₈)₃; and A is anaryl diradical.

In certain embodiments, the invention relates to any of theaforementioned methods, wherein R₁ represents alkyl, fluoroalkyl,cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl,alkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl, —CH₂CH(OH)—R₈,—(CH₂)_(n)—R₈, —C(R₈)═C(R₈)₂, —C≡CR₈, —CH(R₈)₂, or —C(R₈)₃; A is an aryldiradical; and R₄, R₅, R₆, and R₇ represent independently for eachoccurrence methyl, ethyl, or n-butyl.

In certain embodiments, the invention relates to any of theaforementioned methods, wherein R₄, R₅, R₆, and R₇ representindependently for each occurrence methyl, ethyl, or n-butyl.

In certain embodiments, the invention relates to any of theaforementioned methods, wherein the salt is represented by

R₁ represents alkyl, fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl,cycloalkenyl, heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl,heteroaralkyl —CH₂CH(OH)—R₈ or —CH₂CHN(R₈)₂, R₄, R₅, R₆, and R₇represent independently for each occurrence methyl, ethyl, or n-butyl;and R₈ represents alkyl, aryl or aralkyl.

In certain embodiments, the invention relates to any of theaforementioned methods, wherein R₁ represents alkyl, aryl or aralkyl. Incertain embodiments, the invention relates to any of the aforementionedmethods, wherein R₁ represents —CH₂CH(OH)—R₈ or —CH₂CHN(R₈)₂. In certainembodiments, the invention relates to any of the aforementioned methods,wherein R₁ represents alkyl, aryl or aralkyl; and R₄, R₅, R₆, and R₇represent independently for each occurrence methyl, ethyl, or n-butyl.

In certain embodiments, the invention relates to a method of releasing agas, comprising the step of heating a salt; wherein the salt isrepresented by

wherein, independently for each occurrence,

X represents —CO₂ ⁻¹, —CS₂ ⁻¹, —SO₂ ⁻¹ or —NO₂ ⁻¹;

A represents boron tetrafluoride, phosphorus tetrafluoride, phosphorushexafluoride, alkylsulfonate, fluoroalkylsulfonate, arylsulfonate,bis(alkylsulfonyl)amide, bis(fluoroalkylsulfonyl)amide,bis(arylsulfonyl)amide,(fluoroalkylsulfonyl)-(fluoroalkylcarbonyl)amide, halide, nitrate,nitrite, sulfate, hydrogensulfate, alkyl sulfate, aryl sulfate,carbonate, bicarbonate, carboxylate, phosphate, hydrogen phosphate,dihydrogen phosphate, hypochlorite,tris(perfluoroalkyl)trifluorophosphate anion, or an anionic site of acation-exchange resin;

T represents N or P;

E represents —C(═O)— or —S(═O)₂—;

Z represents an aryl or heteroaryl diradical;

R₁ represents alkyl, fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl,cycloalkenyl, heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl,heteroaralkyl, or arylcycloalkyl; wherein said alkyl, fluoroalkyl,cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl,alkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl, or arylcycloalkyl maybe substituted with 1 to 3 substituents selected from the groupconsisting of halogen, azide, alkyl, aralkyl, alkenyl, alkynyl,cycloalkyl, hydroxyl, alkoxyl, amino, nitro, sulfhydryl, imino, amido,phosphonate, phosphinate, carbonyl, carboxyl, silyl, ether, alkylthio,sulfonyl, sulfonamido, ketone, aldehyde, ester, heterocyclyl, aryl,heteroaryl, fluoroalkyl and cyano;

R₈ represents independently for each occurrence —(CH₂)_(n)—CH₃,cycloalkyl, aryl, or heteroaryl;

m represents independently for each occurrence an integer in the range1-10 inclusive; and

n represents independently for each occurrence an integer in the range1-10 inclusive.

In certain embodiments, the invention relates to any of theaforementioned methods, wherein X is —CO₂ ⁻¹.

In certain embodiments, the invention relates to any of theaforementioned methods, wherein A represents I⁻¹, Br⁻¹, Cl⁻¹, HSO₄ ⁻¹,CH₃SO₃ ⁻¹, NO₃ ⁻¹, ClO₃ ⁻¹, FSO₃ ⁻¹, CF₃SO₃ ⁻¹, (CF₃SO₂)₂N⁻¹,tris(perfluoroalkyl)-trifluorophosphate (FAP) anions, or atetrafluoroethylene-perfluoro-3,6-dioxa-4-methyl-7-octenesulfonic acidcopolymer (Naftion).

In certain embodiments, the invention relates to any of theaforementioned methods, wherein T represents N.

In certain embodiments, the invention relates to any of theaforementioned methods, wherein E represents —C(═O)—. In certainembodiments, the invention relates to any of the aforementioned methods,wherein E represents —S(═O)₂—.

In certain embodiments, the invention relates to any of theaforementioned methods, wherein R₁ is alkyl, aryl or aralkyl. In certainembodiments, the invention relates to any of the aforementioned methods,wherein R₁ is alkyl.

In certain embodiments, the invention relates to any of theaforementioned methods, wherein R₃ is hydrogen or alkyl.

In certain embodiments, the invention relates to any of theaforementioned methods, wherein Z is an aryl diradical. In certainembodiments, the invention relates to any of the aforementioned methods,wherein Z is an benzene diradical.

In certain embodiments, the invention relates to any of theaforementioned methods, wherein R₁ represents alkyl, fluoroalkyl,cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl,alkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl, —CH₂CH(OH)—R₈,—(CH₂)_(n)—R₈, —C(R₈)═C(R₈)₂, —C≡CR₈, —CH(R₈)₂, or —C(R₈)₃; and Z is anaryl diradical.

In certain embodiments, the invention relates to any of theaforementioned methods, wherein T represents N; R₁ represents alkyl,fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl,heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl,—CH₂CH(OH)—R₈, —(CH₂)_(n)—R₈, —C(R₈)═C(R₈)₂, —C≡CR₈, —CH(R₈)₂, or—C(R₈)₃; and Z is an aryl diradical.

In certain embodiments, the invention relates to any of theaforementioned methods, wherein the salt is represented by

R₁ represents alkyl, fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl,cycloalkenyl, heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl,heteroaralkyl —CH₂CH(OH)—R₈ or —CH₂CHN(R₈)₂; and R₈ represents alkyl,aryl or aralkyl.

In certain embodiments, the invention relates to any of theaforementioned methods, wherein R₁ represents alkyl, aryl or aralkyl. Incertain embodiments, the invention relates to any of the aforementionedmethods, wherein R₁ represents —CH₂CH(OH)—R₈ or —CH₂CHN(R₈)₂.

EXEMPLIFICATION

The invention now being generally described, it will be more readilyunderstood by reference to the following examples which are includedmerely for purposes of illustration of certain aspects and embodimentsof the present invention, and are not intended to limit the invention.

Example 1

SYNTHESIS OF ZWITTERIONS FOR PROPANESULTONE AND 2,4-BUTANESULTONECOMPOUNDS. The sultone is dissolved in 50 mL toluene. The amine is addedslowly and the solution stirred overnight. The resulting solid isfiltered by vacuum filtration. The crude product is rotary evaporatedand further dried under vacuum. The salt is recrystallized from hotmethanol and dried under vacuum. The product is characterized by ¹H and¹³C NMR.

Example 2

SYNTHESIS OF ZWITTERIONS FOR 1,4-BUTANESULTONE COMPOUNDS. The sultone isdissolved in 50 mL toluene. The amine is added slowly and the solutionrefluxed overnight. The resulting solid is filtered by vacuumfiltration. The crude product is rotary evaporated and further driedunder vacuum. The salt is recrystallized from hot methanol and driedunder vacuum. The product is characterized by ¹H and ¹³C NMR.

Example 3

SYNTHESIS OF AMMONIUM SALTS. The zwitterion is dissolved in 10 mL wateror methanol. Ammonium hydroxide is added and the solution stirred for 30min. The crude product is rotary evaporated and further dried undervacuum. The product is characterized by ¹H and ¹³C NMR

Example 4

WATER SATURATION EXPERIMENTS. Samples of select salts (mostly theresinous/plastic/gel-like materials) were azeotropically dried withbenzene, placed into open vials then stored in vacuo over P₂O₅(s) for 1week. The “dry” mass of each sample was then determined. The open samplevials were then stored in a sealed in a container above a waterreservoir, and the salt masses re-determined and the physical state ofeach material qualitatively assessed at 1, 4, 7 and 14 day intervals.The resulting mass changes were tabulated, and the molar water uptake asa function of time are shown graphically for each salt (see FIGS. 7 and8).

Example 5

REVERSIBLE CAPTURE OF CO₂ WITH A RESINOUS MATERIAL. In order todemonstrate the potential utility of the adhering nature of the plasticor resinous materials, [1B2A3A] was used to create a prototypepass-through device for reversible CO₂ capture (FIG. 2). On exposing theresin to a slow flow of CO₂ for 12 h, it became opaque and frosted inappearance, consistent with CO₂ absorption (vide infra) Subsequentpassage of hot water (˜80° C.) through the coil while subjecting thesample to mechanical vacuum resulted in CO₂ extrusion and a return ofthe resin to its pre-exposure appearance. Remarkably, this compound andthe others like it are the first non-polymeric plastic or resinousmaterials used to capture CO₂, making them potentially valuablecompliments to SAWD technology (see Etoh, T. et al. IntersocietyConference on Environmental Systems; Society of Automotive Engineers:Seattle, Wash., 1987; Technical Paper 871516).

Example 6

SYNTHESIS OF ZWITTERIONS FOR PROPANESULTONE AND 2,4-BUTANESULTONECOMPOUNDS. The sultone is dissolved in 50 mL toluene. The amine is addedslowly and the solution stirred overnight. The resulting solid isfiltered by vacuum filtration. The crude product is rotary evaporatedand further dried under vacuum. The salt is recrystallized from hotmethanol and dried under vacuum. The product is characterized by ¹H and¹³C NMR.

Example 7

SYNTHESIS OF ZWITTERIONS FOR 1,4-BUTANESULTONE COMPOUNDS. The sultone isdissolved in 50 mL toluene. The amine is added slowly and the solutionrefluxed overnight. The resulting solid is filtered by vacuumfiltration. The crude product is rotary evaporated and further driedunder vacuum. The salt is recrystallized from hot methanol and driedunder vacuum. The product is characterized by ¹H and ¹³C NMR.

Example 8

SYNTHESIS OF AMMONIUM SALTS. The zwitterion is dissolved in 10 mL wateror methanol. Ammonium hydroxide is added and the solution stirred for 30min. The crude product is rotary evaporated and further dried undervacuum. The product is characterized by ¹H and ¹³C NMR.

Example 9

SYNTHESIS OF THE ZWITTERION OF PROPANE SULTONE AND3-(DIETHYLAMINO)PROPYLAMINE. A 500 mL round-bottomed flask equipped witha stir bar, reflux condensor and drying tube was charged with 5.01 gpropane sultone (41.0 mmol) and 150 mL of reagent grade toluene. To thissolution was then added 5.34 g of 3-(diethylamino) propylamine (41.0mmol). The solution was stirred at ambient temperature for seven days atwhich time a white precipitate was observed. The white precipitate wasfiltered and washed with diethyl ether (2×, 100 mL) and dried in vacuo,leaving a white solid product (6.63 g, 64%).

Example 10

SYNTHESIS OF 3-(DIETHYLAMINO)-1-(PROPYL-3-SULFONYL)PROPYLAMOONIUMBISTRIFLUOROMETHANESULFOIMIDATE. A 50 mL beaker was charged with 2.69 gof zwitterion product from Example 9 (10.7 mmol), 2.3 mL ofbistrifluoromethanesulfoimide (4.2 M, 9.6 mmol) and 5 ml deionizedwater. A clear, light yellow solution was observed. The solution wasfiltered and the water removed in vacuo, leaving a light yellow, viscousliquid product (5.02 g, 98%).

EQUIVALENTS

Those skilled in the art will recognize, or be able to ascertain usingno more than routine experimentation, many equivalents to the specificembodiments of the invention described herein. It is, therefore, to beunderstood that the foregoing embodiments are presented by way ofexample only and that, within the scope of the appended claims andequivalents thereto, the invention may be practiced otherwise than asspecifically described and claimed.

INCORPORATION BY REFERENCE

All of the US patents and US patent application Publications citedherein are hereby incorporated by reference.

1. A salt represented by:

wherein, independently for each occurrence, W represents an ammoniumcation, a phosphonium cation, a heterocyclic cation, an alkali metalcation or an alkaline earth metal cation; T represents N or P; Yrepresents CH₂, CHF, CF₂ or Z—O—Z; Z represents CH₂, CHF or CF₂; R₁represents hydrogen, alkyl, fluoroalkyl, cycloalkyl, heterocycloalkyl,alkenyl, cycloalkenyl, heterocycloalkenyl, alkynyl, aryl, heteroaryl,aralkyl, heteroaralkyl, or arylcycloalkyl; wherein said alkyl,fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl,heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl,or arylcycloalkyl may be substituted with 1 to 3 substituents selectedfrom the group consisting of halogen, azide, alkyl, aralkyl, alkenyl,alkynyl, cycloalkyl, hydroxyl, alkoxyl, amino, nitro, sulfhydryl, imino,amido, phosphonate, phosphinate, carbonyl, carboxyl, silyl, ether,alkylthio, sulfonyl, sulfonamido, ketone, aldehyde, ester, heterocyclyl,aryl, heteroaryl, fluoroalkyl and cyano; R₂ represents alkyl,fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl,heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl,or arylcycloalkyl; wherein said alkyl, fluoroalkyl, cycloalkyl,heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl, alkynyl,aryl, heteroaryl, aralkyl, heteroaralkyl, or arylcycloalkyl may besubstituted with 1 to 3 substituents selected from the group consistingof halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl,hydroxyl, alkoxyl, amino, nitro, sulfhydryl, imino, amido, phosphonate,phosphinate, carbonyl, carboxyl, silyl, ether, alkylthio, sulfonyl,sulfonamido, ketone, aldehyde, ester, heterocyclyl, aryl, heteroaryl,fluoroalkyl and cyano; R₃ represents hydrogen, alkyl, fluoroalkyl,cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl,alkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl, arylcycloalkyl,bicyclic ring, tricyclic ring, bicyclic or tricyclic fused ring,—(CH₂)_(n)—R₈, —C(═O)OR₈, —C(═O)N(R₈)₂, —C(═O)SR₈, —C(═O)R₈, —C(═NR₈)R₈,—C(═S)R₈, —C(R₈)═C(R₈)₂, —C≡CR₈, —CH(R₈)₂, —C(R₈)₃, or —(CH₂)_(n)—NH₂;R₈ represents independently for each occurrence —(CH₂)_(n)—CH₃,cycloalkyl, aryl, or heteroaryl; m represents independently for eachoccurrence an integer in the range 1-10 inclusive; and n representsindependently for each occurrence an integer in the range 1-10inclusive; or a salt represented by:

wherein, independently for each occurrence, A represents borontetrafluoride, phosphorus tetrafluoride, phosphorus hexafluoride,alkylsulfonate, fluoroalkylsulfonate, arylsulfonate,bis(alkylsulfonyl)amide, bis(fluoroalkylsulfonyl)amide,bis(arylsulfonyl)amide,(fluoroalkylsulfonyl)-(fluoroalkylcarbonyl)amide, halide, nitrate,nitrite, sulfate, hydrogensulfate, alkyl sulfate, aryl sulfate,carbonate, bicarbonate, carboxylate, phosphate, hydrogen phosphate,dihydrogen phosphate, hypochlorite,tris(perfluoroalkyl)trifluorophosphate anion, or an anionic site of acation-exchange resin; T represents N or P; Y represents CH₂, CHF, CF,or Z—O—Z; Z represents CH₂, CHF or CF₂; R₁ represents hydrogen, alkyl,fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl,heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl,or arylcycloalkyl; wherein said alkyl, fluoroalkyl, cycloalkyl,heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl, alkynyl,aryl, heteroaryl, aralkyl, heteroaralkyl, or arylcycloalkyl may besubstituted with 1 to 3 substituents selected from the group consistingof halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl,hydroxyl, alkoxyl, amino, nitro, sulfhydryl, imino, amido, phosphonate,phosphinate, carbonyl, carboxyl, silyl, ether, alkylthio, sulfonyl,sulfonamido, ketone, aldehyde, ester, heterocyclyl, aryl, heteroaryl,fluoroalkyl and cyano; R₂ represents alkyl, fluoroalkyl, cycloalkyl,heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl, alkynyl,aryl, heteroaryl, aralkyl, heteroaralkyl, or arylcycloalkyl; whereinsaid alkyl, fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl,cycloalkenyl, heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl,heteroaralkyl, or arylcycloalkyl may be substituted with 1 to 3substituents selected from the group consisting of halogen, azide,alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, alkoxyl, amino,nitro, sulfhydryl, imino, amido, phosphonate, phosphinate, carbonyl,carboxyl, silyl, ether, alkylthio, sulfonyl, sulfonamido, ketone,aldehyde, ester, heterocyclyl, aryl, heteroaryl, fluoroalkyl and cyano;R₃ represents hydrogen, alkyl, fluoroalkyl, cycloalkyl,heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl, alkynyl,aryl, heteroaryl, aralkyl, heteroaralkyl, arylcycloalkyl, bicyclic ring,tricyclic ring, bicyclic or tricyclic fused ring, —(CH₂)_(n)—R₈,—C(═O)OR₈, —C(═O)N(R₈)₂, —C(═O)SR₈, —C(═O)R₈, —C(═NR₈)R₈, —C(═S)R₈,—C(R₈)═C(R₈)₂, —C≡CR₈, —CH(R₈)₂, —C(R₈)₃, or —(CH₂)_(n)—NH₂; R₄ and R₅represent independently for each occurrence alkyl, fluoroalkyl,cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl,alkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl, arylcycloalkyl,—(CH₂)_(n)—R₈, —C(R₈)═C(R₈)₂—, —C≡CR₈, CH(R₈)₂, or —C(R₈)₃; or R₄ and R₅taken together with the nitrogen to which they are attached form afive-, six-, or seven-membered heterocyclic ring; R₆ represents alkyl,fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl,heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl,arylcycloalkyl, —(CH₂)_(n)—R₈, —C(R₈)═C(R₈)₂, —CH(R₈)₂, or —C(R₈)₃; R₇represents alkyl, fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl,cycloalkenyl, heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl,heteroaralkyl, arylcycloalkyl, —(CH₂)_(n)—R₈, —C(R₈)═C(R₈)₂, —C≡CR₈,—CH(R₈)₂, or —C(R₈)₃; R₈ represents independently for each occurrence—(CH₂)_(n)—CH₃, cycloalkyl, aryl, or heteroaryl; m representsindependently for each occurrence an integer in the range 1-10inclusive; and n represents independently for each occurrence an integerin the range 1-10 inclusive; or a salt represented by:

wherein, independently for each occurrence, W represents an ammoniumcation, a phosphonium cation, a heterocyclic cation, an alkali metalcation or an alkaline earth metal cation; T represents N or P; Erepresents —C(═O)— or —S(═O)₂—; A represents an aryl or heteroaryldiradical; R₁ represents alkyl, fluoroalkyl, cycloalkyl,heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl, alkynyl,aryl, heteroaryl, aralkyl, heteroaralkyl, or arylcycloalkyl; whereinsaid alkyl, fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl,cycloalkenyl, heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl,heteroaralkyl, or arylcycloalkyl may be substituted with 1 to 3substituents selected from the group consisting of halogen, azide,alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, alkoxyl, amino,nitro, sulfhydryl, imino, amido, phosphonate, phosphinate, carbonyl,carboxyl, silyl, ether, alkylthio, sulfonyl, sulfonamido, ketone,aldehyde, ester, heterocyclyl, aryl, heteroaryl, fluoroalkyl and cyano;R₈ represents independently for each occurrence —(CH₂)_(n)—CH₃,cycloalkyl, aryl, or heteroaryl; m represents independently for eachoccurrence an integer in the range 1-10 inclusive; and n representsindependently for each occurrence an integer in the range 1-10inclusive; or a salt represented by:

wherein, independently for each occurrence, A represents borontetrafluoride, phosphorus tetrafluoride, phosphorus hexafluoride,alkylsulfonate, fluoroalkylsulfonate, arylsulfonate,bis(alkylsulfonyl)amide, bis(fluoroalkylsulfonyl)amide,bis(arylsulfonyl)amide,(fluoroalkylsulfonyl)-(fluoroalkylcarbonyl)amide, halide, nitrate,nitrite, sulfate, hydrogensulfate, alkyl sulfate, aryl sulfate,carbonate, bicarbonate, carboxylate, phosphate, hydrogen phosphate,dihydrogen phosphate, hypochlorite,tris(perfluoroalkyl)trifluorophosphate anion, or an anionic site of acation-exchange resin; T represents N or P; E represents —C(═O)— or—S(═O)₂—; Z represents an aryl or heteroaryl diradical; R₁ representsalkyl, fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl,heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl,or arylcycloalkyl; wherein said alkyl, fluoroalkyl, cycloalkyl,heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl, alkynyl,aryl, heteroaryl, aralkyl, heteroaralkyl, or arylcycloalkyl may besubstituted with 1 to 3 substituents selected from the group consistingof halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl,hydroxyl, alkoxyl, amino, nitro, sulfhydryl, imino, amido, phosphonate,phosphinate, carbonyl, carboxyl, silyl, ether, alkylthio, sulfonyl,sulfonamido, ketone, aldehyde, ester, heterocyclyl, aryl, heteroaryl,fluoroalkyl and cyano; R₈ represents independently for each occurrence—(CH₂)_(n)—CH₃, cycloalkyl, aryl, or heteroaryl; m representsindependently for each occurrence an integer in the range 1-10inclusive; and n represents independently for each occurrence an integerin the range 1-10 inclusive.
 2. The salt of claim 1, wherein the salt isrepresented by


3. The salt of claim 1, wherein the salt is represented by


4. The salt of claim 1, wherein W is an ammonium, pyridinium,imidazolium, benzimidazolium, pyrazolium, benzpyrazolium, indazolium,thiazolium, benzthiazolium, oxazolium, benzoxazolium, isoxazolium,isothiazolium, imdazolidenium, guanidinium, quinuclidinium, triazolium,tetrazolium, quinolinium, isoquinolinium, piperidinium, pyrrolidinium,morpholinium, pyridazinium, pyrazinium, piperazinium, triazinium,azepinium, or diazepinium.
 5. The salt of claim 1, wherein W is

R₄ and R₅ represent independently for each occurrence alkyl,fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl,heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl,arylcycloalkyl, —(CH₂)_(n)—R₈, —C(R₈)═C(R₈)₂, —C≡CR₈, —CH(R₈)₂, or—C(R₈)₃; or R₄ and R₅ taken together with the nitrogen to which they areattached form a five-, six-, or seven-membered heterocyclic ring; R₆represents alkyl, fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl,cycloalkenyl, heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl,heteroaralkyl, arylcycloalkyl, —(CH₂)_(n)—R₈, —C(R₈)═C(R₈)₂, —C≡CR₈,—CH(R₈)₂, or —C(R₈)₃; and R₇ represents alkyl, fluoroalkyl, cycloalkyl,heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl, alkynyl,aryl, heteroaryl, aralkyl, heteroaralkyl, arylcycloalkyl, —(CH₂)_(n)—R₈,—C(R₈)═C(R₈)₂, —C≡CR₈, —CH(R₈)₂, or —C(R₈)₃.
 6. The salt of claim 1,wherein T represents N.
 7. The salt of claim 1, wherein Y representsCH₂, CHF or CF₂. 8-9. (canceled)
 10. The salt of claim 1, wherein onlyone Y represents Z—O—Z.
 11. The salt of claim 1, wherein only one Yrepresents Z—O—Z; and Z is CH₂.
 12. The salt of claim 1, wherein onlyone Y represents Z—O—Z; and Z is CF₂.
 13. The salt of claim 1, whereinR₁ is hydrogen.
 14. The salt of claim 1, wherein R₁ represents alkyl,fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl,heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl, orheteroaralkyl. 15-17. (canceled)
 18. The salt of claim 1, wherein R₂ isalkyl, aryl or aralkyl.
 19. (canceled)
 20. The salt of claim 1, whereinR₃ is hydrogen or alkyl.
 21. The salt of claim 1, wherein m is 2 or 3.22-27. (canceled)
 28. The salt of claim 1, wherein the salt isrepresented by


29. The salt of claim 1, wherein the salt is represented by


30. The salt of claim 1, wherein A represents I⁻¹, Br⁻¹, Cl⁻¹, HSO₄ ⁻¹,CH₃SO₃ ⁻¹, NO₃ ⁻¹, ClO₃ ⁻¹, FSO₃ ⁻¹, CF₃SO₃ ⁻¹, (CF₃SO₂)₂N⁻¹,tris(perfluoroalkyl)-trifluorophosphate (FAP) anions, or atetrafluoroethylene-perfluoro-3,6-dioxa-4-methyl-7-octenesulfonic acidcopolymer. 31-51. (canceled)
 52. The salt of claim 1, wherein Erepresents —C(═O)—.
 53. The salt of claim 1, wherein E represents—S(═O)₂—. 54-56. (canceled)
 57. The salt of claim 1, wherein A is anaryl diradical. 58-77. (canceled)
 78. A method of sequestering a gas,comprising contacting the gas with a salt of claim
 1. 79-80. (canceled)81. A method of releasing a gas, comprising the step of heating acomposition comprising a gas dissolved in a salt; wherein the salt isthe salt of claim
 1. 82-95. (canceled)